Marcellus Flow-Back Or Not? a Thesis Submitted To

Identification of Local Ground Water Pollution in Northeastern Pennsylvania: Marcellus Flow-back or Not?

A thesis submitted To Kent State University in partial Fulfillment of the requirements for the Degree of Master of Science

Darren Andrew Reilly

May, 2014

Thesis written by Darren Andrew Reilly B.S., Clarion University of Pennsylvania, 2011 M.S., Kent State University, 2014

Approved by

Anne Jefferson, Advisor

Daniel Holm, Chair, Department of Geology

Janis Crowther, Dean, College of Arts and Sciences

TABLE OF CONTENTS

ACKNOWLEDGEMENTS ...... ix

SUMMARY ...... 1

INTRODUCTION ...... 2

Project Goal and Motivation ...... 2 Sources of Contamination ...... 5 Testing for Contaminants ...... 11

OBJECTIVES ...... 14

STUDY AREA ...... 15

Background ...... 15 Geology ...... 20 Statement of the Problem ...... 25

METHODS ...... 27

Data Sources ...... 27 Historical Ground Water ...... 27 Marcellus Flow-back ...... 28 Animal Waste, Road Salt, & Septic Effluent Contaminated Waters ...... 31 2012-2013 Ground Water Samples ...... 31 Graphical Methods ...... 35 Statistical Methods ...... 39

RESULTS ...... 41

Descriptive Statistic Results for Ground Water ...... 41 Descriptive Statistic Results for Flow-back & Other Contaminated Samples ...... 49 Graphical Results for Ground Water & Contaminated Water Groups ...... 60 Box and Whisker Plots ...... 60 Piper Diagrams...... 63 Stiff Diagrams ...... 74 Cross-plot Mixing Model ...... 80 Statistical Results...... 84 Analysis of Variance...... 84

iii

Discriminant Analysis ...... 86

DISCUSSION ...... 91

Interpretations ...... 91 Limitations ...... 96 Future Work/Recommendations ...... 97

CONCLUSION ...... 98

WORKS CITED ...... 100

APPENDIX 1. Historical Ground Water Data ...... 110

APPENDIX 2. Marcellus Shale Flow-back Data ...... 133

APPENDIX 3. Animal Waste, Septic Effluent, and Road Salt Data ...... 137

APPENDIX 4. 2012-2013 Ground Water Sample Data ...... 148

LIST OF FIGURES

1. ILLUSTRATION OF A MARCELLUS WELL ...... 10

2. LOCATION MAP FOR THE STUDY AREA ...... 16

3. PHYSIOGRAPHIC PROVINCES OF PENNSYLVANIA ...... 18

4. LAND COVER MAP ...... 19

5. GEOLOGIC FORMATION MAP ...... 24

6. EXAMPLE OF A FORM 26R SUBMISSION ...... 30

7. BOX & WHISKER PLOT EXPLANATION ...... 37

8. PIPER DIAGRAM OF WATER TYPE LOCATION ...... 37

9. QUANTILE BOX & WHISKER PLOT...... 62

10. LOCK HAVEN PIPER DIAGRAM ...... 64

11. CATSKILL PIPER DIAGRAM ...... 65

12. MARCELLUS SHALE FLOW-BACK PIPER DIAGRAM ...... 66

13. ANIMAL WASTE PIPER DIAGRAM ...... 68

14. SEPTIC TANK EFFLUENT PIPER DIAGRAM ...... 69

15. ROAD SALT PIPER DIAGRAM ...... 70

16. PIPER DIAGRAM OF ALL CONTAMINANT TWO-STANDARD-DEVIATION ZONES ...... 71

17. 2012-2013 GROUND WATER PIPER DIAGRAM...... 73

18. STIFF DIAGRAM OF LOCK HAVEN, CATSKILL, & 2012-2013 SAMPLES ...... 75

19. STIFF DIAGRAM OF FLOW-BACK, ANIMAL WASTE, SALT, & SEPTIC EFFLUENT ...... 75

20. STIFF DIAGRAMS OF 2012-2013 SAMPLES ...... 77

21. CL/BR VS. CL CROSS-PLOT ...... 82

22. CL/BR VS. CL CROSS-PLOT, WITH NON-DETECT NE PA SAMPLES ...... 83

23. CL CONCENTRATIONS OF 2012-2013 SAMPLES WITH DISTANCE TO NEAREST GAS WELL ...... 95

LIST OF TABLES

1. STRATIGRAPHIC CHART OF ROCK IN NE PA ...... 23

2. LIST OF MAJOR IONS, TRACEMETALS, NUTRIENTS, AND PHYSICAL PROPERTIES...... 34

3. LOCK HAVEN: NUMBER OF SAMPLES, DETECTIONS, AND QUANTILE CONCENTRATIONS ...... 44

4. CATSKILL: NUMBER OF SAMPLES, DETECTIONS, AND QUANTILE CONCENTRATIONS ...... 45

5. LOCK HAVEN & CATSKILL WELLS THAT EXCEED EPA DRINKING WATER STANDARDS ...... 46

6. 2012-2013: NUMBER OF SAMPLES, DETECTIONS, AND QUANTILE CONCENTRATIONS ...... 47

7. 2012-2013: GROUND WATER WELLS THAT EXCEED EPA DRINKING WATER STANDARDS ...... 48

8. FLOW-BACK: NUMBER OF SAMPLES, DETECTIONS, AND QUANTILE CONCENTRATIONS ...... 52

9. FLOW-BACK: SAMPLES THAT EXCEED EPA DRINKING WATER STANDARDS ...... 53

10. SEPTIC CONTAMINATED: NUMBER OF SAMPLES, DETECTIONS, AND QUANTILE CONCENTRATIONS ...... 54

11. SEPTIC CONTAMINATED: SAMPLES THAT EXCEED EPA DRINKING WATER STANDARDS ...... 55

12. ANIMAL CONTAMINATED: NUMBER OF SAMPLES, DETECTIONS, AND QUANTILE CONCENTRATIONS ...... 56

13. ANIMAL CONTAMINATED: SAMPLES THAT EXCEED EPA DRINKING WATER STANDARDS ...... 57

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14. SALT CONTAMINATED: NUMBER OF SAMPLES, DETECTIONS, AND QUANTILE CONCENTRATIONS ...... 58

15. SALT CONTAMINATED: SAMPLES THAT EXCEED EPA DRINKING WATER STANDARDS ...... 59

16. TDS QUANTILE VALUES FOR BOX & WHISKER PLOT ...... 62

17. FLOW-BACK & GROUND WATER TDS MIXTURE CONCENTRATION ... 62

18. ANOVA ION COMPARISON TABLE ...... 85

19. DISCRIMINANT ANALYSIS 1 CLASSIFICATION RESULTS ...... 89

20. 2012-2013 SAMPLE PROBABILITY OF FALLING INTO A CERTAIN GROUP FOR DISCRIMINANT ANALYSIS 1 ...... 89

21. DISCRIMINANT ANALYSIS 2 CLASSIFICATION RESULTS ...... 90

22. 2012-2013 SAMPLE PROBABILITY OF FALLING INTO A CERTAIN GROUP FOR DISCRIMINANT ANALYSIS 2 ...... 90

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ACKNOWLEDGEMENTS

As with any major accomplishment, this project could not have been finished without the help of others. First, I would like to thank my advisor Anne Jefferson for her encouragement to keep things simple. I would also like to thank her for providing helpful suggestions and guidance that led to the completion of this project. Second, but equally important, I would like to thank my former advisor Yoram Eckstein, for his continuous support, as well as the guidance and constructive criticism he provided.

I would also like to thank my co-advisor David Singer, for his thoughtful insights and suggestions to the geochemical data and data presentation that were used in this project. Additionally, I would like to thank my readers, Joseph Ortiz and Neil Wells, for their critical review of, and helpful suggestions to, the manuscript.

A special thanks goes to all 21 homeowners who took time to let me collect ground water samples. Without your help I could have never completed this project.

I would like to thank Lori Davias, of the Tioga County Conservation District, for spreading information about my project to residents in the area, in addition to members of the Pine Creek Watershed. Thanks to Lori, I was able to obtain several samples in Tioga

County, PA.

Similarly, I would like to thank my friends at the U.S. Geological Survey in

Williamsport, PA for their assistance finding sites for me to sample in Lycoming

County, PA. They were also helpful at recommending sampling protocols and field advice.

I would like to thank Seewald Laboratory and Ray Martrano for giving me a discount on sample analysis. Without this discount I would have been limited to a much smaller sample size.

Additionally, I would like to thank Dennis J. Low of the U.S. Geological Survey,

New Cumberland, PA; and Victoria Neboga of the Department of Conservation and

Natural Resources Bureau of Topographic and Geological Survey, Middletown, PA.

They clarified whether the background water well samples were filtered or unfiltered.

They also provided information on what organization would use filtered vs. unfiltered samples, and its implication on the data.

Most importantly I would like to thank my family for their support. I thank my

Uncle, John Wilson of the U.S. Geological Survey, who helped me find relevant literature and datasets and was always willing to answer technical questions and offer suggestions. I also thank my brother, Lucas, for his assistance editing this manuscript.

Finally, I thank my parents for their constant encouragement. They were instrumental in helping me acquire sample sites in Bradford and Sullivan County, for which I am very grateful.

SUMMARY

Using graphical and statistical methods, geochemical data from 21 allegedly contaminated ground water wells in northeastern Pennsylvania were compared with data from historical ground water, Marcellus flow-back fluid, and other contaminated waters.

The graphical methods included box and whisker plots, Piper diagrams, Stiff diagrams, and Cl/Br vs. Cl cross-plots. The statistical methods included summary statistics, analysis of variance, and discriminant analysis. The geochemical data collected for this study included the following major ions, trace metals, nutrients, and physical properties: sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), barium (Ba), strontium

(Sr), manganese (Mn), iron (Fe), aluminum (Al), chloride (Cl), bromide (Br), sulfate

(SO4), arsenic (As), nitrate-nitrite as N, total Kjeldahl nitrogen, total nitrogen, alkalinity, and total dissolved solids (TDS).

The graphical and statistical results show that none of the 2012-2013 ground water wells were detectably impacted by flow-back fluids. Instead, the results show that at least one well is contaminated with animal waste or septic effluent. Discriminant analysis of the 2012-2013 ground water samples supports this observation. The remaining wells are geochemically similar to historical ground water wells both graphically and statistically. These findings suggest that the major and trace element geochemistry of northeastern Pennsylvania ground water has not been detectably influenced by flow-back fluid spills at these 21 sites.

INTRODUCTION

Project Goal and Motivation

Northeastern Pennsylvania has rapidly evolved over the past five years from an area with very little, if any, natural gas drilling, to the most productive shale gas region within the entire Marcellus shale play, causing concerns about environmental safety. One issue that has caught the attention of homeowners and media is the possibility that flow- back fluids from the drilling and fracturing process have contaminated private water wells. The goal of this thesis is to investigate the water chemistry of residential well water in four northeastern Pennsylvania counties – Bradford, Tioga, Lycoming, and

Sullivan – in order to assess the likelihood of contamination from various sources. In doing so, my research will shed light on conflicting hypotheses voiced by two stakeholders in the study area. These hypotheses are that:

1. Local ground water resources are contaminated by flow-back fluids from shale

gas fracturing operations, as contended by some residents;

2. Local ground water resources are not contaminated by flow-back fluids from

shale gas fracturing operations, as contended by the gas-drilling industry.

In the United States more than 18 billion gallons (70 billion liters) of ground water are consumed daily from both public and residential water wells (Kenny et al.,

2009). Public ground water withdrawals are defined as any water well that supplies water

2 to at least 25 people, or has a minimum of 15 connections (Kenny et al., 2009). In 2005, public water wells supplied clients with 14.6 billion gallons (55 billion liters) of water daily (Kenny et al., 2009). In order to ensure the public has safe water, this water must meet certain drinking water standards set by the United States Environmental Protection

Agency [EPA], covering 103 different elements, chemical compounds, and physical conditions (U.S. EPA, 2009). The majority of these substances (88) fall under primary drinking water regulations, which are legally enforceable standards for public water systems (U.S. EPA, 2009). Typically, long term exposure to concentrations above the

EPA primary drinking water standards will cause negative health effects (U.S. EPA,

2009). The remaining substances fall under secondary drinking water regulations, which are non-enforceable recommendations regarding contaminants in drinking water that may cause cosmetic or aesthetic effects, such as iron staining or metallic taste (U.S. EPA,

2009).

Compared to public water wells, residential water wells are not required to meet

EPA drinking water standards and are non-enforceable. In 2005, residential water wells provided 42.9 million people, or 14% of the United States population, with water, resulting in the withdrawal of 3.7 billion gallons per day (14 billion liters per day)

(Kenny et al., 2009). Homeowners with residential wells are responsible for regularly testing and interpreting their well water for potential contaminants.

When homeowners suspect water well contamination, chemistry is often the best method to determine if there is a problem and, if so, how severe it may be. Appropriate chemical analysis of well water may even identify the source of the contamination. A

3 targeted suite of chemical analysis is also helpful when determining what type of well- head treatments might be effective at mitigating the aesthetic or health problems, and can potentially identify the parties responsible for the ground water contamination (Musgrove et al., 2011).

Over the last several decades, sophisticated methods beyond simple elemental chemistry analysis have been developed, and new chemical compounds have been identified to detect and trace ground water contaminants. For example, contaminant specific chemicals like optical brighteners are an effective method for identifying ground water contaminated by septic tank effluent (Hanchar, 1991). Geophysical techniques like electrical conductivity surveys have also been used to identify and locate road salt contamination plumes (Risch and Robinson, 2000). Additionally, the use of isotopic data such as stable-isotope ratios of hydrogen and oxygen, stable isotopes of nitrogen, and isotope ratios of strontium have been used to identify ground water contamination, water- rock interactions, origin, and mixing (Musgrove et al., 2011). Finally, some ground water investigations now analyze for pesticides, trace organic contaminants, and human-health pharmaceuticals due to emerging concerns over specific agricultural, industrial, and urban pollutants (Shelton et al., 2010).

These more sophisticated methods used to identify and trace ground water contaminants have proven to be a valuable tool for governmental agencies, large corporations, and university researchers who can afford such tests. However, for many homeowners, a standard set of chemistry analyses is often the best choice. Chemical analysis has several advantages to the average homeowner, since commercial laboratories

4 are readily available and offer reasonable rates. Depending on the location of the water well, a local laboratory might recommend testing for certain ions. For example in

Pennsylvania, a basic water test might include: total coliform with E. coli, pH, turbidity, hardness, nitrate, TDS, iron, lead, copper, and chloride. A chemical analysis for these analytes would cost $150 to $200. This water analysis offers an affordable first step that, if anomalous or elevated values are found, could be expanded to test for other chemicals.

Sources of Contamination

Nationally the most common threats to ground water quality are underground storage tanks, agricultural activity, municipal landfills, and surface impoundments

(Fetter, 1993). However, in rural America the prevalent ground water contaminants for residential wells include: septic system effluent, barnyard runoff, pesticides and fertilizers, salt, methane gas, and oil spills (Waller, 1994). Septic systems are commonplace in rural areas. This is especially true in Pennsylvania, which has more rural residents than any other state, with approximately one quarter of all homes using on-lot septic systems (Fleeger, 1999). If homeowners fail to regularly maintain their septic tanks, it can become a source of pollution (Fleeger, 1999). Common septic pollutants include elevated concentrations of chloride, sulfate, ammonia, nitrate-nitrite as N, organic nitrogen, total phosphate, fecal coliform bacteria, fecal streptococci bacteria, and total organic carbon (Hanchar, 1991). Other septic contaminants might include numerous household chemicals like bleach, ammonia, detergents, and other toxic materials (Waller,

1994).

Barnyard runoff of animal waste is another common contaminant source in rural areas. Animal waste has the potential to enter ground water and result in elevated concentrations of fecal coliform and streptococci bacteria, total nitrogen, ammonia, phosphate, chloride, total dissolved solids, and total organic carbon (Kreis et al., 1972).

Similar farm contaminants include pesticides and fertilizers. In Pennsylvania, research has shown that 27% of surveyed wells in corn producing regions had at least one type of pesticide present at detectible levels (Swistock et al., 2003). The pesticides present in ground water include atrazine, 2,4-dichlorophenoxyacetic acid, chlorpyrifos “dursban”, glyphosate, metolachlor, and simazine (Swistock et al., 2003). Artificial fertilizers are a major contributor of nitrogen and phosphate to ground water, resulting in EPA exceedances in 20% of shallow rural wells (wells that are less than 100 feet or 30 meters below the water table) (Dubrovsky et al., 2010).

Salt is also a prevalent contaminant of rural ground water in regions that experience winter weather. Salt contamination can occur in areas where large stockpiles of road salt are stored, or areas near salted roadways. The main ground water contaminants from road salt are sodium and chloride (Watson et al., 2002). However, if halite road salt is not used a common alternative is calcium chloride road salt, which will result in elevated concentrations in calcium (Watson et al., 2002).

Unlike salt contamination, which results primarily from human activities, natural gas originates from natural sources. Natural gas contamination is possible from numerous formations in the United States, consisting of either methanogenic or thermogenic gas

(Waller, 1994). In northeastern Pennsylvania it has been long known that methane gas is

6 present in shallow formations, but recent studies have determined that valley wells have more methane than upland wells (Molofsky et al., 2011).

Finally, oil spills are another potential ground water contaminant that rural well owners might experience. For example, many rural homes heat with oil, which increases the potential for accidental spills or tank failures and, could permanently contaminate local ground water (Waller, 1994). Oil contaminants could contribute polycyclic aromatic hydrocarbons and other toxic substances to ground water (Fetter, 1993).

Although rural ground water has been threatened by all of these contaminants, a new threat has caught the public’s attention: spilled or leaking flow-back fluids from

Marcellus shale fracturing. The development of the Marcellus shale play in

Pennsylvania’s Bradford, Tioga, Lycoming, and Sullivan Counties has been quite dramatic over the past several years, going from nearly zero drilled wells in 2006 to nearly 3,000 drilled wells in 2013 (Pennsylvania Department of Environmental

Protection [PADEP] Spud Data Report, 2013). Prior to this boom, the area had been explored several times over the past 150 years, yet no significant oil and gas deposits were deemed economically viable (Heverly, 1918). However, in 2007, horizontal drilling and hydraulic fracturing were used in this region for the first time, proving the Marcellus shale as a highly prolific gas producer. Horizontal drilling and hydraulic fracturing had made the previously uneconomical Marcellus shale economical.

Horizontal drilling is the process where energy companies drill down vertically until they reach a desired depth, called the kick-off point (U.S. Department of Energy

[U.S. DOE], 2009). There, they begin to rotate the drill bit horizontally for several

7 hundred feet (meters) until the bit is completely horizontal within the target formation

(Figure. 1) (U.S. DOE, 2009). This gives companies thousands of feet of pay zone to hydraulically fracture. Hydraulic fracturing uses on average 99.5% water and sand and

0.5% chemical additives to fracture rock under high pressure, allowing the trapped gas to flow to the surface (U.S. DOE, 2009). A typical Marcellus well requires around 5 million gallons (19 million liters) of fresh water to fracture the shale, of which 10-30 percent returns to the surface as flow-back (Chesapeake Energy, 2012; Rassenfoss, 2011). This means somewhere between 0.5-1.5 million gallons (1.9-5.7 million liters) of flow-back water will return to the surface in a relatively short amount of time. On average, the majority of flow-back volume will return to the surface in under seven days following completion, compared to formation brine from conventional (non-shale/non-horizontal) wells, which is produced for the life of the well (U.S. DOE, 2009).

This flow-back has very high concentrations of total dissolved solids (TDS), averaging 160,000 milligrams per liter (mg/l), with varying concentrations of fracturing chemicals. Some of the more abundant dissolved solids include sodium, magnesium, calcium, strontium, barium, and chloride. In addition, some of the chemicals used include petroleum distillate, ethylene glycol, sodium polycarboxylate, magnesium peroxide, and citric acid (Frac Focus, 2013). Therefore, flow-back water must be properly handled and disposed of to prevent contamination of surface and ground waters.

In Pennsylvania, flow-back is handled in numerous ways. On-site, the flow-back can be stored in 20,000 gallon steel tanks (75,700 liter tanks), pumped to plastic lined impoundment ponds, or recycled for future use (PADEP Marcellus Shale Development,

2013). Off-site, flow-back can be trucked away to a water recycling plant specifically designed for flow-back waters, or trucked away to an injection disposal well (PADEP

Marcellus Shale Development, 2013). With all of these various storage, recycling, and disposal methods, potential exists for tears in plastic liners, leaks/breaks in pipes, and truck accidents, all which result in flow-back entering the environment. Additionally, flow-back can enter the environment if there is a well failure, in either the casing or the blow-out preventer.

Figure 1. Illustration of a typical horizonal Marcellus well (from: http://marcellus.psu.edu/resources/maps.php)

Testing for Contaminants

Once the most likely ground water contaminants have been identified, appropriate geochemical testing can identify the source of contamination. For example, if a basic ground water analysis was conducted for total coliform with E. coli, pH, turbidity, hardness, nitrate, TDS, iron, lead, copper, and chloride, it would not be very effective at pinpointing the contaminant source. This basic test would only provide information on whether or not the ground water is free of bacteria and common contaminants. In order to identify sources of ground water contamination, homeowners can either test for characteristic ions when they suspect a specific type of contamination, or test for a laundry list of chemicals when the source is unknown.

Some of the specific contaminant ions might include conservative tracers like bromide, chloride, and iodide, along with sodium and total nitrogen. These ions were used by Panno et al. (2006), Whittemore (2007), and Katz et al. (2010) to create distinct graphs that could identify zones most likely affected by septic effluent, animal waste, road salt, landfill leachate, basin brines, and field tile effluent. If homeowners tested their wells for these same ions and compared their results to the Panno et al. (2006) results, they might be able to rule out or confirm contamination from many of the potential sources of rural contamination. However, the average homeowner likely would not know what their chemistry results mean in terms of contaminant level and source. Also, if the homeowner doesn’t have knowledge of the background ion chemistry for their specific aquifer, it would be impossible to compare their results and determine differences.

Ultimately, it may be possible for ion chemistry to characterize and distinguish different

11 contaminant sources, but it depends on the homeowner to properly analyze the results, and to take any corrective steps to ensure their drinking water is safe.

For contamination concerns related to Marcellus shale fracturing and flow-back, several methods have been used to identify potential contaminants. Some of these methods include isotopes, methane, and ion chemistry. For example in northeastern

Pennsylvania, Osborn et al. (2011) found that carbon and hydrogen isotopes of methane can be used to indicate potential methane contamination from nearby natural gas wells.

The same isotopes were used in the EPA’s study at Pavillion, Wyoming, which determined that thermogenic gas was entering shallow domestic wells (DiGiulio et al.,

2011). 87Sr/86Sr ratios have been shown to be potentially useful for tracing Marcellus shale flow-back fluids but to date they have not been used in the field (Chapman et al.,

2012). Simple measurements of methane in ground water have also been used to identify areas of potential pollution, although this is highly controversial, since methane is naturally common in many water wells in northeastern Pennsylvania (Molofsky et al.,

2011). Next, the use of ion chemistry has also been determined useful when identifying potential contamination sites from fracturing and flow-back. For example the EPA used ion chemistry to detect elevated concentrations of potassium and chloride in two deep monitoring wells near active oil and gas wells near Pavillion, Wyoming (DiGiulio et al.,

2011). The EPA also detected benzene, xylenes, gasoline range organics, diesel range organics, and total purgeable hydrocarbons in shallow ground water wells in close proximity to former holding pits for fluids and solids near Pavillion, Wyoming (DiGiulio et al., 2011).

In northeastern Pennsylvania, a growing number of homeowners are claiming that their ground water is being contaminated by nearby Marcellus shale activities; however, other potentially more common sources of rural pollution are also present. It is the goal of this thesis to investigate the water chemistry of residential well water in northeastern

Pennsylvania, in order to assess the source of ground water contamination, with a particular focus on whether flow-back water is detectable in residential well water.

OBJECTIVES

In order to accomplish the goal of this project, which involves investigating water chemistry from residential wells in the study area, in order to assess the likelihood of contamination from various sources, this project must achieve several key objectives. The objectives are to:

1. Collect and analyze water samples from residential water wells in the four

counties and use historical data to chemically characterize local fresh ground

water resources.

2. Characterize the chemistry of flow-back fluids, produced in the study area, by

identifying characteristic major and trace ion and ionic ratios, and compare it to

other common ground water contaminants like road salt, animal waste, and septic

effluent.

3. Assess possible contamination of residential well water using graphical and

statistical methods.

STUDY AREA

Background

The study area of Bradford, Tioga, Lycoming, and Sullivan Counties in

Pennsylvania (Figure 2) was selected because of recent, widespread claims of ground water contamination caused by natural gas drilling. Claims of ground water contamination were most prevalent in 2009, 2010, and 2011 when drilling was most intense. These claims have garnered national and international media attention, spurring investigations by the United States Geological Survey [Baseline Groundwater Quality from 20 Domestic Wells in Sullivan County, Pennsylvania, 2012], the Environmental

Protection Agency [Study of the Potential Impacts of Hydraulic Fracturing on Drinking

Water Resources, 2012], the Pennsylvania Department of Environmental Protection [PA

DEP and Cabot Oil & Gas Consent Order and Settlement Agreement, 2010], and numerous academics [Methane contamination of drinking water accompanying gas-well drilling and hydraulic fracturing, 2010].

Figure 2. Location map of the study area, including elevation and major roadways.

Physiographically, the study area is situated within the Appalachian Plateaus

Province, or more specifically, within the Glaciated Low Plateau Section, Glaciated High

Plateau Section, and Deep Valleys Section (Figure 3) (Commonwealth, 2000). Annual precipitation in the study area averages 36 inches (91 cm), all of which falls within the

Susquehanna River Basin (Fleeger, 1999). The major water bodies in northeastern

Pennsylvania include four major rivers and two reservoirs. The major river watersheds include the Tioga River, which flows into the Chemung River, which flows into the

Susquehanna River; then downstream the West Branch Susquehanna River also flows into the Susquehanna River (USGS National Land Cover, 2011). The two reservoirs are both located in northern Tioga County and include the Cowanesque Reservoir and Tioga-

Hammond Reservoir (USGS National Land Cover, 2011).

Bradford and Sullivan County had a population of 62,622 and 6,428 respectively in 2010 (U.S. Census, 2011). Tioga and Lycoming County had a population of 41,981 and 116,111 respectively in 2010 (U.S. Census, 2011). Together, these four counties cover an area of 3,994 square miles (10,344 km2), with a total population of 227,142

(PennDOT, 2011). This equates to a population density of 57 people per square mile (22 people per km2), which is considerably lower than the rural classification cutoff of 274 people per square mile (105 people per km2), established by the Center for Rural

Pennsylvania (PA Office of Rural Health, 2013). This area’s rural nature is also reflected by its land use patterns (Figure 4). Land use consists of forest, 61%; agriculture fields,

17%; water, 10%; and fields, 7% (USGS National Land Cover, 2011). Urban areas make up only 5% of the study area (USGS National Land Cover, 2011).

Figure 3. Physiographic provinces of PA with study area outlined (Commonwealth, 2000).

Figure 4. Land cover in the study area.

Geology

The bedrock in the study area is primarily composed of upper Devonian shales, mudstones, siltstones, and sandstones, overlain by varying thicknesses of glacial and fluvial sediments. Devonian-aged rock comprises roughly 70 % of all exposed rock within the study area (PA Bureau, 2001). The main Devonian strata are the Lock Haven and Catskill Formations, which account for ~27.5% and 31.5% of all rock exposed in the study area, respectively (PA Bureau, 2001). The minor bedrock formations that crop out include Ordovician, 2%; Silurian, 2%; Devonian, 70% (as stated above); Mississippian,

21%; and Pennsylvanian, 5% (Table 1) (PA Bureau, 2001). However, only Devonian and

Mississippian strata were part of this study (Figure 5).

The Lock Haven Formation is composed of predominantly light olive gray interbedded fossiliferous marine mudstones, shales, siltstones, sandstones, and a few thin beds of conglomerate (Taylor, 1984). The Lock Haven Formation consists of detrital sediments from mixed fluvial-deltaic and linear clastic shorelines, interspersed with thin open-marine carbonates that were deposited during eustatic sea-level rises (Harper,

1999). Fine grained rocks compose roughly 70% of the formation, and the formation is commonly crossed by numerous fractures and joints, which promote ground water flow

(Taylor, 1984). The Lock Haven thickens toward the east of the study area, where it is approximately 4,000 feet thick (1,219 meters) (Taylor, 1984).

The Catskill Formation is composed of green, red, and gray nonmarine detrital rock (Harper, 1999). The formation consists of a succession of greenish-gray and grayish- red, fine- to coarse-grained sandstone and mostly grayish-red siltstone and shale (Taylor

20 et al., 1983). Some gray sandstone and conglomerate are also present (Taylor, 1984). The

Catskill’s upper and lower contacts are gradational, being recognized by the higher percentage of red rock in the Catskill (Harper, 1999). The depositional environment consists of mixed continental, fluvial-deltaic, and marginal-marine settings (Harper,

1999). The formation has been divided into five mappable units within the Appalachian

Basin: which are the Irish Valley Member; Sherman Creek Member; the undivided

Popular Gap and Packerton Members; Buddys Run Member; and Duncannon Member

(Taylor et al., 1983). The formation is commonly crossed by numerous fractures and joints, which promote the flow of ground water. The Catskill ranges in thickness from

1,900 feet (580 meters) in central Pennsylvania to 8,600 feet (2,621 meters) in eastern

Pennsylvania (Harper, 1999).

The minor formations include the Devonian Trimmers Rock Formation, the

Devonian Onondaga and Old Port Formations, and the Devonian and Mississippian

Huntley Mountain Formation. The middle and upper section of the Trimmers Rock

Formation is a medium gray to olive gray interbedded shale, siltstone, and fine-grained sandstone, while the lower 100 feet (30 meters) is grayish-black shale. The Trimmers

Rock can be as thick as 2,500 feet (762 meters) (Taylor, 1984). The Onondaga Formation is composed of roughly 50 feet (15 meters) of gray argillaceous limestone, with interbeds of shale (Taylor, 1984). The Old Port Formation is a laterally variable unit consisting of discontinuous sequences of limestone, sandstone, shale, and chert. It ranges in thickness from 50 to 100 feet (15 to 30 meters) (Taylor, 1984). The Huntley Mountain Formation consists of greenish-gray to olive-gray, fine grained, flaggy sandstone, with interbeds of

21 red claystone (Berg, 1999). The Huntley Mountain Formation ranges in thickness from

500 to 700 feet (152 to 213 meters) (Berg, 1999).

The Lock Haven and Catskill Formations are the primary ground water aquifers for the region. The water table in northeastern Pennsylvania varies physiographically; however, it generally mimics topography. For example, the median well depth in the

Lock Haven Formation is 140 feet (43 meters) for the Glaciated Low Plateau, 110 feet

(34 meters) for the Glaciated High Plateau, and 100 feet (30 meters) for the Deep Valleys

Section (Fleeger et al., 2004). The median well depth in the Catskill formation is 225 feet

(69 meters) for the Glaciated Low Plateau, 163 feet (50 meters) for the Glaciated High

Plateau, and 123 feet (37 meters) for the Deep Valleys Section (Fleeger et al., 2004).

Well yields for both formations are usually adequate for domestic use and also vary physiographically (Figure 3). The median well yield for the Lock Haven Formation is 10 gal/min (38 L/min) for the Glaciated Low Plateau, 16 gal/min (60 L/min) for the

Glaciated High Plateau, and 10.5 gal/min (40 L/min) for the Deep Valleys Section

(Fleeger et al., 2004). The median well yield for the Catskill formation is 20 gal/min (76

L/min) for the Glaciated Low Plateau, 20 gal/min (76 L/min) for the Glaciated High

Plateau, and 10 gal/min (38 L/min) for the Deep Valleys Section (Fleeger et al., 2004).

On average, the higher well yields of the Catskill are caused by the presence of coarser sediments, compared to the finer grained, lower yield Lock Haven. Fractures and joints in both formations also promote ground water flow, greatly increasing well yields compared to similar unfractured formations.

Table 1. Stratigraphic chart of rocks in NE Pennsylvania (Taylor, 1984).

Age Unit Geologic Description - Poorly to well-sorted deposits of glacial and Alluvium

nary fluvial clay, silt, sand, gravel, and boulders.

Quarter

Allegheny & Pottsville Group Shale, sandstone, and thin beds of limestone Undivided and coal. Upper unit is composed of sandstone, siltstone, Pottsville Group thin coal beds, and conglomerate; lower unit is Pennsylvanian dominantly sandstone. Upper unit is composed of light gray calcareaous quartz sandstone; the lower unit

Mauch Chunk Formation consists of interbedded sandstone, siltstone, shale, and mudstone. Upper unit is composed of light gray, fine- to medium-grained orthoquartzite; the lower unit Burgoon Sandstone

is gray sandstone with some interbedded Mississippian sandstone, shale, and mudstone. Gray sandstone and some thin beds of grayish- Huntley Mountain Formation red siltstone. Duncannon Member Grayish-red sandstone, siltstone, and shale with Catskill Sherman Creek Member some gray sandstone and conglomerate; Formation sandstone layers are generally fine grained and Irish Valley Member thick bedded, commonly fractured. Light-olive-gray interbedded sandstone, Lock Haven Formation siltstone, and shale; a few beds of conglomerate occur near the top, commonly fractured. Interbedded light-olive-gray shale, siltstone, Brallier Formation

Upper Devonian and some sandstone. Harrell Formation Dark-gray to black shale; generally very fissile. Interbedded medium-gray to olive-gray Trimmers Rock Formation siltstone, shaly-siltstone, and shale. Tully Limestone Olive- to medium-gray, fossiliferous shaly Member limestone or calcareous shale. Mahantango Upper Member Formation Medium- to dark-gray shale with minor Hamilton Middle Member amounts of siltstone and limestone. Group Lower Member Dark-gray to black shale, very fissile, Marcellus Formation homogeneous, carbonaceous shale containing locally abundant pyrite. Middle Middle Devonian Very fine grained to crystalline, light- to dark- Onondaga Formation brownish-gray, somewhat argillaceous and cherty limestone.

Figure 5. Geologic formations where water samples were collected.

Statement of the Problem

In Northeastern Pennsylvania, a growing number of homeowners claim that natural gas operations have contaminated their water wells. However, to date, no energy company has explicitly acknowledged responsibility for contaminating water wells. They claim that the contamination is a result of local ground water bedrock geology. However, some companies’ actions either suggest otherwise, or at least indicate that keeping the public happy is their most convenient course of action. For example, energy companies have purchased several properties from homeowners who claimed water well contamination. Additionally, a growing number of homes are receiving fresh water from energy companies. This is easily noticeable, since plastic tanks called “water buffaloes” sit outside these supposedly contaminated homes.

Although these examples provide only anecdotal evidence, the Pennsylvania

Department of Environmental Protection has documented several cases of Marcellus shale flow-back spills (PADEP Oil and Gas Compliance Report, 2013). For example, on

November 23, 2009 in Armenia Township, Bradford County, an operator spilled approximately 6,000 gallons (22,710 liters) of flow-back water into a nearby wetland

(PADEP fines Talisman, 2010). Another incident occurred March 2011 at a flow-back water recycling plant in Williamsport, Lycoming County, where 800 to 1,000 gallons

(3,028 to 3,785 liters) of flow-back fluid were spilled due to human error (PADEP fines

Terraqua, 2012). As a result, up to 250 gallons (946 liters) of fluid entered a storm drain that discharged into the West Branch of the Susquehanna River (PADEP fines Terraqua,

2012). Another incident occurred April 19, 2011 in Leroy Township, Bradford County,

25 when an operator lost control of a well head while hydraulic fracturing, causing 10,000 gallons (37,850 liters) of water to breach containment and flow into an unnamed tributary of Towanda Creek (PADEP fines Chesapeake, 2012). Stream measurements on April 20 recorded elevated levels of total dissolved solids, chloride, and barium where the tributary enters Towanda Creek (PADEP fines Chesapeake, 2012). These are prime examples of surface and ground water pollution caused by flow-back. Considering the glacial history of the area and the presence of fractured bedrock (see Table 1), contaminants have the potential to migrate relatively fast, permitting widespread dispersion of contaminant plumes.

The accidental release of flow-back water into the environment is well documented; however, in northeastern Pennsylvania, flow-back is not the only type of ground water pollutant and is definitely not the most common. Common contaminants in the area include: road salt, septic tank effluent, and animal waste fertilizer (Mullaney et al., 2009). Since contamination can potentially originate from any one of these sources, it is important to be able to identify the major contaminant. This can be achieved by identifying distinct chemical differences among flow-back, road salt, septic tank effluent, and animal waste (Panno et al., 2006). Once these contaminants are classified into distinct groups, it becomes possible to determine whether or not flow-back water is the culprit. From these results it will be possible to implement best management practices so water wells are properly protected.

METHODS

Data Sources

Historical Ground Water

Water well data for historical ground water wells were obtained from the

Pennsylvania Geological Survey’s Water Resource Reports 56 (Taylor et al., 1983) and

58 (Taylor, 1984), and the U.S. Geological Survey’s report on Selected Ground Water

Quality Data in Pennsylvania 1979-2006 (Low et al., 2008). The Pennsylvania

Geological Survey reports were originally published in 1983 and 1984, in cooperation with the Susquehanna River Basin Commission (Taylor et al., 1983; Taylor, 1984). These reports consist of samples collected during 1981 and 1982 that were analyzed for major cations, anions, trace metals, and nutrients only. The USGS report was produced in cooperation with the Pennsylvania Department of Environmental Protection, and included 11 major analyte groups (Low et al., 2008). These major analyte groups included: major ions, minor ions, microorganisms, nutrients, pesticides, fungicides, herbicides, insecticides, radiochemicals, volatiles, and physical properties (Low et al.,

2008) However, this thesis used only the major ion, minor ion, nutrient, and physical property groups, because they contained a sufficient number of samples, and were frequently the only analytes tested in older samples (Table 2). The USGS sample results

27 were also broken-up into filtered and unfiltered results. For this thesis, unfiltered samples were preferred; however, for some samples of chloride, sulfate, and bromide filtered samples were used because no unfiltered samples existed. Unfiltered samples were chosen because these samples represent concentrations a well owner would have to deal with. Also, unfiltered samples are preferred by Pennsylvania state agencies and the EPA for most of their enforcement regulations (D. J. Low, personal communication, February

4, 2013). In total, 340 partial and complete sample results were collected for the study area (Appendix 1).

Marcellus Flow-back

Marcellus shale flow-back data were obtained from a Pennsylvania Department of

Environmental Protection file review of Form 26R, which is a “chemical analysis of residual waste annual report by the generator” (Figure 6). Every operator in Pennsylvania producing Marcellus waste—in this case, liquid waste—is required to submit a Form 26R which includes a “detailed chemical characterization of the waste” (PADEP Bureau of

Waste Management, 2012). Examination of more than 500 Form 26R’s revealed only 27 reports with the required chemical analysis (Appendix 2). Using the well name, municipality, and county information provided on the Form 26R, the exact coordinates for each well could be identified by searching for the well on the PA DEP spud data report webpage. The content of these reports typically were very detailed and consisted of major cations, anions, trace metals, nutrients, volatile organic compounds, radiological parameters, and physical properties. However, this thesis only used the major cations,

28 anions, trace metals, nutrients, and physical properties, in order to make comparisons with available ground water data.

Figure 6. Example of a Form 26R submission, edited for privacy.

Animal Waste, Road Salt, and Septic Effluent Contaminated Waters

Data on ground waters contaminated by animal waste, road salt, and septic effluent were collected from various USGS, EPA, state, and university reports (Hanchar,

1991; Robertson et al., 1991; Risch & Robinson, 2000; Jagucki & Darner, 2001; Watson et al., 2002; Kreis et al., 1972; Panno et al., 2006). This data also came from various locations, including the states of Texas, Tennessee, Indiana, Illinois, Ohio, and the province of Ontario. Although none of this data was from northeastern Pennsylvania, it was assumed that these results should be comparable to contaminated ground water in the area (Panno et al., 2006). The compiled data from these reports often did not analyze for every ion that this study was interested in; however, most samples did include the major cations and anions. Another problem with this data was that the contaminant concentrations had varying degrees of dilution in ground water, creating large ranges in concentrations. This made the use of specific ratios more useful than concentration values for distinguishing contaminated zones. In the end, this study was able to use data from 23 animal waste samples, 60 road salt samples, and 43 septic effluent samples (Appendix 3).

2012 – 2013 Ground Water Samples

Well water samples from northeastern Pennsylvania were collected in Bradford,

Tioga, Lycoming, and Sullivan counties from well owners who suspected some type of water contamination (Appendix 4). Samples were solicited over a period of two months through advertisements in five local newspapers, as well as social media outlets

31 frequented by environmentalists. Of those who responded to these advertisements, only people with perceived water-quality problems were included, while those who responded looking for a free water analysis and had no current water issues were rejected. The first ground water sample was collected on December 18, 2012, and the last sample was collected on February 23, 2013. Of the 21 samples collected, 13 of the well owners claimed to have abnormal color, odor, or taste prior to nearby drilling, while 8 well owners believed their water issues started after or concurrent with nearby Marcellus activity.

From the 21 samples collected, 10 were from Bradford County, 8 were from

Tioga County, 2 were from Lycoming County, and 1 was from Sullivan County. By plotting the location of these wells on the geologic map it was determined that 18 of the

21 samples draw water from either the Lock Haven or Catskill Formation. This determination was based on the assumption that the well was not drawing water from alluvial material, but was screened in the uppermost bedrock aquifers. This assumption was validated from four water well logs that were available, which showed that each well was completed in bedrock.

Samples were collected using modified USGS field methods (U.S. Department of the Interior, U.S. Geological Survey, 2006). First, the site was inspected for safety hazards—such as a confined space—and appropriate measures were taken on a site specific basis. Second, the well was purged for at least five minutes in order to flush the pressure tank and pipe of stagnant water. Purging the well of three casing volumes of water was not necessary, because it was assumed the homeowner regularly used water for

32 showering, toilets, dishwashing, and other uses that would have removed three casing volumes. Third, the sample was withdrawn from the closest point to the well, which typically was at the base of the pressure tank, and was then placed into prepared sample bottles. This point was chosen because water collected here hadn’t yet encountered any filter systems or any housing pipe that might influence results. This location is also where natural gas companies and laboratory technicians collect water samples.

Finally, the sample location, date, and time of sampling was recorded on the chain of custody form, and then the sample was put on ice or kept refrigerated until analysis by

Seewald Laboratory located in Williamsport, PA. All samples were delivered to the lab before the hold time of seven days was met, and there were no issues with the samples.

Quality assurance and quality control reports were not included in the reports for these samples, but lab-wide protocols were followed and specified data quality was assured.

Each sample was analyzed for the following major ions, trace metals, nutrients, and physical properties: sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), barium

(Ba), strontium (Sr), manganese (Mn), iron (Fe), aluminum (Al), chloride (Cl), bromide

(Br), sulfate (SO4), arsenic (As), nitrate-nitrite as N, total Kjeldahl nitrogen, total nitrogen, alkalinity, and total dissolved solids (TDS) (Table 2). The laboratory methods used to analyze each of these ions, along with their detection limits, are also listed in

Table 2.

Table 2. List of major ions, trace metals, nutrients, and physical properties. Along with the selected method of analysis, and the detection limits. Major Cations Method Detection Limit Sodium - Na+ EPA 200.7 0.05, 0.5 Potassium - K+ EPA 200.7 0.5 Calcium - Ca2+ EPA 200.7 0.01, 0.1 Magnesium - Mg2+ EPA 200.7 0.01, 0.1 Barium - Ba2+ EPA 200.7 0.01 Strontium - Sr2+ EPA 200.7 0.01 Manganese - Mn2+ EPA 200.7 0.01 Iron - Fe2+ EPA 200.7 0.01 Aluminum - Al3+ EPA 200.7 0.02 Major Anions Chloride - Cl- EPA 300.0 0.5, 0.9, 1 Bromide - Br- EPA 300.0 0.1 2- Sulfate - SO4 EPA 300.0 0.9, 1.8 Trace Metal Arsenic - As EPA 200.8 0.001 Nutrients Nitrate-Nitrite as N EPA 353.2 0.2, 0.3 SM 4500 Norg B / Total Kjeldahl Nitrogen 0.84 SM 4500 NH3 B&C Total Nitrogen Calculation 0.89 Physical Properties

Alkalinity as CaCO3 EPA 310.2 2, 10 Total Dissolved Solids SM 2540 C 5, 10, 20

Graphical Methods

In order to characterize and distinguish between historical 1980s ground water, contaminated ground water, flow-back fluids, and 2012-2013 ground water, several graphical methods were used. These methods include box and whisker plots, Piper diagrams, Stiff diagrams, and cross-plot diagrams. Each of these graphical methods have been successfully used to analyze and interpret water quality for decades, and continue to be useful today.

Box and whisker plots were constructed for the 1980s Lock Haven, 1980s

Catskill, and 2012-2013 ground water samples, as well as Marcellus shale flow-back samples. These box and whisker plots were created in order to see where the 2012-2013 ground water samples plot in relation to historical ground water, and flow-back concentrations. The box and whisker plots were constructed in JMP 9, and used the quantile box and whisker plot in order to include all values. The quantile plot is constructed using values where the pth quantile is larger than the p% of the values, so for the 10th quantile 10% of the samples lie below it (Figure 7). For these comparisons, TDS concentrations were used, since TDS is a good indicator of general water quality.

Piper diagrams were constructed for 1980s Catskill, 1980s Lock Haven, and

2012-2013 ground water samples, as well as flow-back, road salt, septic effluent, and animal waste contaminated waters using values for major cations and anions. These diagrams were created in an Excel macro developed by Keith Halford of the U.S.

Geological Survey (1999). This program allows the user to input cation and anion data in

35 milligrams per liter, and automatically converts these values into percent milliequivalent per liter.

Piper diagrams visually show where samples lie with respect to the major cation and anion chemistry, and identify the primary water type of each group (Figure 8). For each group, individual points were plotted, the mean was plotted, and a two-standard- deviation polygon around the mean was created. The group mean also identifies the region where the majority of samples should plot, and the main water type. The two- standard-deviation ovals were created by using the group average for cations and anions, changing one ion at a time plus and minus two-standard-deviations. The objective for creating two-standard-deviation ovals was to determine if they could be used to distinctly separate the ground water groups from the flow-back and contaminated waters.

Maximum

97.5% Quantile

90% Quantile 75% Quantile 50% Quantile

25% Quantile

10% Quantile

2.5% Quantile

Minimum

Figure 7. Explanation of box and whisker plot.

Figure 8. Location of the primary water types on the Piper diagram.

Stiff diagrams were created for each ground water group, the Marcellus flow-back group, and each contaminant group. These diagrams were created in order to verify the results from the Piper diagrams, since some of the samples couldn’t be plotted on the

Piper diagrams due to missing anion or cation data. The exclusion of some samples due to incomplete datasets may have also altered the group averages plotted on the Piper diagrams. The Stiff diagrams avoided this potential problem by using average values for each cation and anion. This method included all samples with detected ions.

The final graphical method was a Cl/Br vs. Cl cross-plot of all available 1980s

Catskill, 1980s Lock Haven, 2012-2013 ground water samples, flow-back, animal waste, septic effluent, and road salt samples. Two cross-plots were constructed, and included one with only the 2012-2013 samples with detectable levels of bromide, while the second included 2012-2013 samples with non-detectable levels of bromide at half the detection limit. These graphs are discussed further in the results section. The Cl/Br vs. Cl cross-plot has been used in numerous studies (Panno et al., 2006; Whittemore, 2007; Katz et al.,

2010) and is a successful method for creating separation among various contaminant groups. However, for this study, it was only important that the Marcellus flow-back group plot distinctly from the other contaminants, in order to determine whether flow- back had contaminated ground water. The construction of a flow-back mixing model was also used in order to see if any of the contaminated or ground water samples approached this group.

Statistical Methods

Statistical methods were used to answer two questions. First, are the 1980s Lock

Haven and Catskill ground water statistically similar? Second, are any of the 2012-2013 ground water samples impacted from flow-back or other contaminants? In order to answer this first question, an analysis of variance test was conducted. For the second question, discriminant analysis was selected due to its ability to assign an unknown sample to a specific group. For both statistical tests the original data was converted to log normalized data using the straight transformation equation log(X + 10 – Xsmallest) (Lowry,

2014). This transformation allowed the data to have a more Gaussian distribution, which helped minimize the effect of outliers and skewness on the analysis (Lowry, 2014).

An analysis of variance (ANOVA) test was conducted for the Catskill and Lock

Haven ground water samples in order to determine if ionic chemistry was statistically different, or whether chemical results from the two aquifers could be grouped. The phrase

“analysis of variance” comes from the method of analyzing variability within the entire data set to see how much can be attributed to differences between means and how much is due to variability in the individual population (Peck et. al., 2012). The ANOVA test compares two or more population means relative to the variance in each group. If the majority of cations and anions among the two groups are statistically similar—meaning the null hypothesis that the two concentration means are equal has been accepted—then it might be appropriate for both datasets to be combined into one ground water group.

However, if the alternate hypothesis that the two means differ is accepted, it may be best to keep the ground water groups separate.

Discriminate analysis provides a method for distinguishing between ground water, animal waste, septic effluent, road salt, and Marcellus flow-back groups. This type of analysis is structured similarly to analysis of variance, based on the way in which variances and covariances can be divided among categories or groups (Davis, 2002).

There is a matrix of total variances and covariances, as well as a matrix of pooled within- group variances and covariances (Poulsen & French, 2013). These two matrices are compared through multivariate F tests, which determine whether or not there are any significant differences in variables between groups (Poulsen & French, 2013). Once the group means are found to be statistically different, discriminant analysis determines an optimal combination of variables, so the first discriminant function provides the most overall discrimination between the groups, while the second discriminant function provides the second most (Poulsen & French, 2013). Next, a canonical correlation analysis is performed that will calculate the successive functions and canonical roots, which will be used to classify samples. Finally, the samples get classified into the groups in which they had the closest discriminant scores (Poulsen & French, 2013).

One advantage of the discriminant analysis test is that samples coming from an unknown group can be classified into one of the discriminant groups. It was for this reason that discriminant analysis was used to identify the 2012-2013 ground water samples. Assuming that the 2012-2013 samples belong to one of the ground water or contaminant groups, and not some unanalyzed contaminant group, then these samples should fall into one of the groups.

RESULTS

Descriptive Statistic Results for Ground Water Samples

Ground water data from northeastern Pennsylvania can be broken down into two main groups, historical 1980s Lock Haven and Catskill ground water samples, and 2012-

2013 ground water samples. All ground water samples were analyzed for sixteen different constituents, which included major ions, trace metals, nutrients, and physical properties. This list includes: sodium (Na), potassium (K), calcium (Ca), magnesium

(Mg), barium (Ba), strontium (Sr), manganese (Mn), iron (Fe), aluminum (Al), chloride

(Cl), bromide (Br), sulfate (SO4), arsenic (As), nitrate-nitrite as N, alkalinity, and total dissolved solids (TDS).

Comparing the 1980s Lock Haven and Catskill water quality, the three most commonly EPA exceeded ions include aluminum, manganese, and iron. These ions are not harmful; however they are aesthetically undesirable, since they leave a metallic taste in the water and can stain clothing and sinks. Also after examining each ion’s quantile concentration range for Lock Haven and Catskill samples, it becomes evident that the

Lock Haven has on average higher concentrations than the Catskill aquifer (Table 3 & 4).

These ion concentration differences are primarily caused by the difference in lithology between the Lock Haven and Catskill.

1980s Lock Haven ground water quality can be classified as “moderately hard” to

“hard.” The aluminum concentration is elevated above the secondary drinking water standards in roughly 57% of all wells, while manganese and iron concentrations are high in 51 and 44% of wells, respectively (Table 5). The Lock Haven also has elevated concentrations of TDS in 12% of wells, and elevated chloride in 6% of wells, both of which are secondary water regulations. None of the wells had concentrations of sulfate above, the secondary drinking water standard. Additionally, Lock Haven ground water wells exceed EPA primary drinking water standards for barium in 7% of the wells, and arsenic in 9% of the wells (Table 5). None of the wells had elevated concentrations of nitrate-nitrite as N, which is a primary drinking water standard.

The 1980s Catskill ground water can be classified as “soft” to “moderately hard”.

The only ion commonly in excess is aluminum, which is elevated in 66% of the wells

(Table 5). Iron and manganese concentrations are elevated in 24 and 26% of Catskill water wells. Total dissolved solids are elevated in 7% of wells, while chloride is only elevated in 1% of wells, and none of the wells exceed secondary drinking water standards for sulfate. For the primary drinking water standards, barium is elevated in nearly 6% of wells, while arsenic is elevated in 6% of wells (Table 5). None of the Catskill wells had elevated concentrations of nitrate-nitrite as N.

The 2012-2013 ground water samples, predominantly from the Catskill and Lock

Haven Formations, commonly displayed ion concentration ranges that were between the

1980s Lock Haven and Catskill quantile concentration ranges (Table 6). These ground water samples can be classified as “moderately hard” to “hard” water. The 2012-2013

42 samples commonly exceeded EPA secondary drinking water standards for manganese, iron, and aluminum, similar to the historical ground water (Table 7). However, unlike the

1980s ground water data, concentrations of arsenic in modern samples were likely to exceed the EPA maximum contaminant level in 14% of wells, which is notably higher than the historic ground water data. Similarly, concentrations of nitrate-nitrite as N were elevated in 5% of wells, compared to 0% in historic ground water wells. The remaining secondary and primary drinking water contaminants of chloride, sulfate, TDS, barium, and strontium were not exceeded in any of the wells.

Table 3. Lock Haven: number of samples, detections, and quantile concentrations. [NA, not analyzed; --, not applicable. All benchmarks and guidelines are in milligrams per liter (mg/L).] Physical property, Concentration at set percentiles Maximum Number of Number of nutrient, major ion, or Concentration or samples detections trace element 10th 25th Median 75th 90th value Physical Property (mg/L)

Alkalinity as CaCO3 97 97 85.6 124 170 211 256 346 Nutrient (mg/L) Nitrate-Nitrite as N 85 82 0.02 0.02 0.04 0.4 1.45 4.4 Trace Element (mg/L) Arsenic 178 29 0.004 0.007 0.013 0.03 0.054 0.117 Major Ions (mg/L) Aluminum 154 110 0.04 0.06 0.09 0.13 0.33 1.6 Barium 67 46 0.1 0.2 0.3 0.63 1.7 17.2 44 Bromide 14 14 0.15 0.2 0.2 0.33 0.45 0.5

Calcium 166 166 14.4 26.6 39 54.7 66.7 199 Chloride 172 171 2 3 8 21 124.2 1080 Iron 166 160 0.04 0.09 0.24 0.69 1.79 15.91 Magnesium 166 166 3.87 5.98 8.95 12.33 16.76 41.1 Manganese 164 138 0.02 0.03 0.08 0.25 0.57 6.07 Potassium 166 166 0.6 0.96 1.5 2.37 3.39 7.9 Sodium 166 166 5.54 7.4 15.85 44.75 106.6 763.8 Strontium 83 78 0.04 0.09 0.18 0.49 1.1 14 Sulfate 179 169 7 10 20 30 42 210 TDS 95 95 141.6 180 246 306 512.8 1706

Table 4. Catskill: number of samples, detections, and quantile concentrations. [NA, not analyzed; --, not applicable. All benchmarks and guidelines are in milligrams per liter (mg/L).] Physical property, Concentration at set percentiles Maximum Number of Number of nutrient, major ion, or Concentration or samples detections trace element 10th 25th Median 75th 90th value Physical Property (mg/L)

Alkalinity as CaCO3 83 83 19.4 58 112 156 218.4 328 Nutrient (mg/L) Nitrate-Nitrite as N 79 79 0.02 0.1 0.46 1.24 2.64 6.38 Trace Element (mg/L) Arsenic 109 19 0.004 0.005 0.006 0.023 0.045 0.072 Major Ions (mg/L) Aluminum 100 86 0.03 0.06 0.09 0.14 0.48 24 Barium 18 16 0.07 0.1 0.2 0.98 2.03 2.1 45 Bromide 1 1 ------0.1

Calcium 103 103 6.88 15.3 31.1 40.9 52.16 240 Chloride 106 106 2 3 7.5 22.75 45.6 304 Iron 103 102 0.04 0.05 0.1 0.31 1.02 56.4 Magnesium 103 103 1.5 2.6 4.1 7.7 13.52 45.6 Manganese 103 81 0.01 0.01 0.03 0.1 0.31 7.37 Potassium 103 103 0.48 0.7 1.1 2.3 3.75 10.3 Sodium 103 103 1.68 4.7 10.3 28.2 96.18 233.7 Strontium 22 18 0.03 0.06 0.12 0.45 1.07 1.74 Sulfate 106 90 5 5 10 20 39.8 250 TDS 83 83 67.6 108 162 254 373.2 874

Table 5. Lock Haven and Catskill wells that exceed EPA secondary and primary drinking water standards. [MCLs are U.S. EPA Maximum Contaminant Levels for public water supplies; SDWRs are Secondary Drinking Water Regulations that are non- enforceable guidelines regarding cosmetic or aesthetic effects in drinking water; HBSLs are Health-Based Screening Levels developed by the USGS using EPA toxicity data and methods; --, not applicable. All benchmark and guideline values are in milligrams per liter.]

Benchmark or guideline Human-health benchmark Non-health guideline Nutrient, major ion, and trace element Wells exceeding Wells exceeding Value Type Value Type benchmarks (Percent) guideline (Percent) Lock Haven Catskill Lock Haven Catskill Nutrients (mg/L) Nitrate-Nitrite as N 10 MCL 0 0 ------Trace Element (mg/L) Arsenic 0.01 MCL 9 6 ------

46 Major ions (mg/L)

Aluminum ------0.05 to 0.2 SDWR 57 66 Barium 2 MCL 7 6 ------

Chloride ------250 SDWR 6 1 Iron ------0.3 SDWR 44 24

Manganese 0.3 HBSL 19 8 0.05 SDWR 51 26 Sulfate ------250 SDWR 0 0

Strontium 4 HBSL 5 0 ------TDS ------500 SDWR 12 7

Table 6. 2012-2013 ground water: number of samples, detections, and quantile concentrations. [NA, not analyzed; --, not applicable. All benchmarks and guidelines are in milligrams per liter (mg/L).] Physical property, Concentration at set percentiles Maximum Number of Number of nutrient, major ion, or Concentration or samples detections trace element 10th 25th Median 75th 90th value Physical Property (mg/L)

Alkalinity as CaCO3 21 21 70.38 112 173 207 271.2 396 Nutrient (mg/L) Nitrate-Nitrite as N 21 7 0.45 0.48 1.64 5.15 14.1 14.1 Trace Element (mg/L) Arsenic 21 10 0.001 0.001 0.004 0.011 0.047 0.051 Major Ions (mg/L) Aluminum 21 5 0.02 0.02 0.02 0.42 0.53 0.53

47 Barium 21 21 0.05 0.06 0.22 0.53 0.98 1.46 Bromide 21 3 0.14 0.14 0.18 0.35 0.35 0.35 Calcium 21 21 12.54 20.35 31.8 65.85 82.26 86.6 Chloride 21 21 2.44 2.79 10.5 29.6 70.24 93.9 Iron 21 19 0.02 0.05 0.09 0.38 1.3 1.98 Magnesium 21 21 3.25 5.14 8.35 11.85 22.68 31 Manganese 21 14 0.02 0.04 0.09 0.39 1.79 2.06 Potassium 21 20 0.88 1.3 1.85 2.32 4.11 4.27 Sodium 21 21 2.44 9.75 31.6 51.2 83.26 124 Strontium 21 21 0.09 0.16 0.6 1.19 1.7 2.66 Sulfate 21 20 1.75 6.37 13.85 25.5 80.3 109 TDS 21 21 30.6 96 232 311 407.2 432

Table 7. 2012-2013 ground water samples that exceed EPA secondary and primary drinking water standards.

[MCLs are U.S. EPA Maximum Contaminant Levels for public water supplies; SDWRs are Secondary Drinking Water Regulations that are non-enforceable guidelines regarding cosmetic or aesthetic effects in drinking water; HBSLs are Health-Based Screening Levels developed by the USGS using EPA toxicity data and methods; --, not applicable. All benchmark and guideline values are in milligrams per liter.]

Benchmark or guideline Human-health benchmark Non-health guideline Nutrient, major ion, and trace element Wells exceeding Wells exceeding Value Type Value Type benchmarks (Percent) guideline (Percent) Nutrients (mg/L) Nitrate-Nitrite as N 10 MCL 5 ------Trace Elements (mg/L) Arsenic 0.01 MCL 14 ------Major ions (mg/L)

48 Aluminum ------0.05 to 0.2 SDWR 10

Barium 2 MCL 0 ------

Chloride ------250 SDWR 0 Iron ------0.3 SDWR 24

Manganese 0.3 HBSL 19 0.05 SDWR 43 Strontium 4 HBSL 0 ------

Sulfate ------250 SDWR 0 TDS ------500 SDWR 0

Descriptive Statistic Results for Flow-back and Other Contaminated Samples

Background Contaminant data was also compiled for flow-back fluids, septic tank effluent, animal waste, and road salt affected waters, in order to identify concentration ranges and common EPA exceedances. As mentioned in the methods section this data is a conglomeration of samples from various locations in North America, spanning several decades and is assumed to be representative of similar contaminated samples in northeastern Pennsylvania. Each contaminant group was analyzed for the same ions as the ground water samples, in order to make comparisons among contaminated and uncontaminated ground water.

Examining the concentration ranges from the flow-back samples, it is immediately obvious that most of the values are extremely high (Table 8). In fact, the median TDS value of 152,000 ppm is more than four times the average seawater concentration, and more than 700 times the average ground water concentration. Looking at the list of EPA primary and secondary drinking water contaminants, the ions of barium, strontium, chloride, iron, and TDS are exceeded in 100% of samples (Table 9).

Manganese is also elevated in 88% of all flow-back samples. Compared to the previous ions aluminum is only elevated in 35% of samples. The remaining ions of arsenic, nitrate- nitrite as N, and sulfate are only exceeded in 9%, 5%, and 4% of samples, respectively

(Table 9). However, the exceedance percentage of arsenic is likely underestimated because 21 of the samples had detection levels above the EPA maximum contaminant level, which potentially censored some of the samples.

For septic effluent affected ground water it appears that major ion concentrations of calcium, magnesium, potassium, sodium, chloride, and nitrate-nitrite as N, are noticeably higher than 1980s background water samples (Table 10). Looking at the secondary drinking water standards for septic effluent, the most commonly exceeded ions are manganese, iron, and chloride, which are elevated in 41%, 23%, and 16% of wells, respectively (Table 11). The percentage of septic effluent affected wells exceeding the

EPA standard for chloride is significantly higher than 1980s ground water. The concentration of sulfate and TDS were not elevated in any of the samples. The primary drinking water standard for nitrate-nitrite as N was exceeded in 11% of septic effluent affected wells, which is greater than 0% for 1980s ground water (Table 11). Barium was not elevated in any samples, and arsenic was not analyzed. Based on the percentage of wells that were elevated in chloride and nitrate-nitrite as N, these two ions may serve as a good indicators of septic effluent affected ground water.

The animal waste affected ground waters have elevated levels of calcium, magnesium, potassium, sodium, chloride, alkalinity, and TDS (Table 12). These elevated ions are similar to those from septic tank effluent, but their concentrations were always greater in animal waste samples. Some of the commonly exceeded secondary drinking water standards are TDS, manganese, chloride, and iron (Table 13). TDS and manganese are elevated in 100% and 55% of all wells, respectively. Concentrations of chloride and iron in animal waste affected ground waters are elevated in 43% and 18% of wells, respectively. Comparing these percentage exceedances to the 1980s ground water, it is clear that TDS and chloride concentrations are much greater for animal waste influenced

50 ground water, and may be good indicators of contamination. Surprisingly, none of the samples had concentrations above the EPA primary drinking water standard for nitrate- nitrite as N; however, median concentrations are slightly greater than uncontaminated ground water.

Road salt contaminated ground waters have elevated concentrations of calcium, chloride, sodium, and TDS (Table 14). These elevated concentrations make sense since the salt could be either CaCl or NaCl type, and TDS will increase with higher concentrations of dissolved salt. TDS and chloride concentrations in road salt contaminated wells often exceed EPA secondary drinking water standards in 80% and

47% of wells, respectively (Table 15). These elevated concentrations are much greater than uncontaminated ground water, and chloride is even higher than the animal waste and septic effluent samples. The remaining commonly exceeded ions of manganese and iron are elevated in 36% and 30% of wells, which is in range with 1980s ground water (Table

15).

Table 8. Flow-back: number of samples, detections, and quantile concentrations. [NA, not analyzed; --, not applicable. All benchmarks and guidelines are in milligrams per liter (mg/L).] Physical property, Concentration at set percentiles Maximum Number of Number of nutrient, major ion, or Concentration or samples detections trace element 10th 25th Median 75th 90th value Physical Property (mg/L)

Alkalinity as CaCO3 24 21 20 30.5 88 116 172.6 224 Nutrient (mg/L) Nitrate-Nitrite as N 22 6 0.13 0.14 0.37 6.15 22 22 Trace Element (mg/L) Arsenic 23 2 0.038 -- 0.328 -- 0.617 0.617 Major Ions (mg/L) Aluminum 23 9 0.04 0.15 0.42 8.2 36.2 36.2 Barium 26 26 470.16 1257.5 4235 7706.25 12512.7 16715.4

Bromide 19 18 73.18 392.5 522.5 903.75 1055.7 1980 Calcium 27 27 2113.94 6160 8514.5 18682.3 21580 31900 Chloride 26 26 18773.6 57675 89723.5 132750 190600 228000 Iron 27 27 15.7 31 52.5 75.4 103.52 280 Magnesium 27 25 311.8 545 745 1379.83 1610 1940 Manganese 26 23 0.71 2.1 3.42 5.72 12.9 72.8 Potassium 4 4 59.6 101.37 240.91 262.85 265.42 265.42 Sodium 27 27 9057.12 22000 28792 50500.7 70160 78400 Strontium 27 27 559.78 1890 3150 3840 8337.76 10196.4 Sulfate 25 6 7 16.75 28.5 100.25 257 257 TDS 26 26 28873.6 93275 152000 230063 334200 358000

Table 9. Flow-back samples that exceed EPA secondary and primary drinking water standards.

Benchmark or guideline Human-health benchmark Non-health guideline Nutrient, major ion, and trace element Wells exceeding Wells exceeding Value Type Value Type benchmarks (Percent) guideline (Percent) Nutrients (mg/L) Nitrate-Nitrite as N 10 MCL 5 ------Trace Elements (mg/L) Arsenic 0.01 MCL 9 ------Major ions (mg/L)

53 Aluminum ------0.05 to 0.2 SDWR 35 Barium 2 MCL 100 ------

Chloride ------250 SDWR 100 Iron ------0.3 SDWR 100

Manganese 0.3 HBSL 88 0.05 SDWR 88 Strontium 4 HBSL 100 ------

Sulfate ------250 SDWR 4 TDS ------500 SDWR 100

Table 10. Septic contaminated ground water: number of samples, detections, and quantile concentrations. [NA, not analyzed; --, not applicable. All benchmarks and guidelines are in milligrams per liter (mg/L).] Physical property, Concentration at set percentiles Maximum Number of Number of nutrient, major ion, or Concentration or samples detections trace element 10th 25th Median 75th 90th value Physical Property (mg/L)

Alkalinity as CaCO3 41 41 120.4 188 316 409 503.4 608 Nutrient (mg/L) Nitrate-Nitrite as N 9 6 0.1 0.78 1.45 9.9 33 33 Trace Element (mg/L) Arsenic NA NA NA NA NA NA NA NA Major Ions (mg/L) Aluminum NA NA NA NA NA NA NA NA Barium 31 31 0.02 0.03 0.05 0.08 0.15 0.4

Bromide 34 29 0.05 0.07 0.09 0.19 0.36 1.04 Calcium 43 43 29.4 58 70 105 119.2 495 Chloride 43 43 22.08 39.7 69.1 116 319.2 5620 Iron 39 24 0.01 0.04 0.18 0.8 1.51 2.93 Magnesium 43 43 5.88 8.5 23 26 44.2 300 Manganese 39 24 0.01 0.03 0.1 0.2 0.66 0.82 Potassium 43 43 1.62 6 14 21 31 345 Sodium 43 43 19 46 82 115 340.6 2740 Strontium 34 34 0.11 0.15 0.26 0.3 0.72 5.65 Sulfate 43 43 22.8 34 56 92 108.2 130 TDS 7 7 231 306 361 412 414 414

Table 11. Septic contaminated ground water samples that exceed EPA secondary and primary drinking water standards. [MCLs are U.S. EPA Maximum Contaminant Levels for public water supplies; SDWRs are Secondary Drinking Water Regulations that are non-enforceable guidelines regarding cosmetic or aesthetic effects in drinking water; HBSLs are Health-Based Screening Levels developed by the USGS using EPA toxicity data and methods; --, not applicable; NA, not analyzed. All benchmark and guideline values are in milligrams per liter.] Benchmark or guideline Human-health benchmark Non-health guideline Nutrient, major ion, and trace element Wells exceeding Wells exceeding Value Type Value Type benchmarks (Percent) guideline (Percent) Nutrients (mg/L) Nitrate-Nitrite as N 10 MCL 11 ------Trace Elements (mg/L) Arsenic 0.01 MCL NA ------Major ions (mg/L)

55 Aluminum ------0.05 to 0.2 SDWR NA

Barium 2 MCL 0 ------

Chloride ------250 SDWR 16 Iron ------0.3 SDWR 23

Manganese 0.3 HBSL 8 0.05 SDWR 41 Strontium 4 HBSL 3 ------

Sulfate ------250 SDWR 0 TDS ------500 SDWR 0

Table 12. Animal contaminated ground water: number of samples, detections, and quantile concentrations. [NA, not analyzed; --, not applicable. All benchmarks and guidelines are in milligrams per liter (mg/L).] Physical property, Concentration at set percentiles Maximum Number of Number of nutrient, major ion, or Concentration or samples detections trace element 10th 25th Median 75th 90th value Physical Property (mg/L)

Alkalinity as CaCO3 20 20 305.85 410.5 592 761 849 1028 Nutrient (mg/L) Nitrate-Nitrite as N 9 9 0.01 0.06 0.36 1.96 7.51 7.51 Trace Element (mg/L) Arsenic NA NA NA NA NA NA NA NA Major Ions (mg/L) Aluminum NA NA NA NA NA NA NA NA Barium 11 11 0.05 0.09 0.11 0.2 0.39 0.42

56 Bromide 11 11 0.09 0.11 0.15 0.22 0.49 0.52

Calcium 23 23 109.4 127 173 218 645.6 1619 Chloride 23 23 37.4 56 186 308 400 648 Iron 11 3 0.01 0.01 0.48 8.3 8.3 8.3 Magnesium 23 23 20.8 32 45 70 95.6 117 Manganese 11 7 0.01 0.06 0.41 0.61 0.67 0.67 Potassium 23 22 2 2.75 106 258.5 629.3 1352 Sodium 23 23 16.2 45 113 150 332.4 655 Strontium 11 11 0.14 0.18 0.2 0.35 0.52 0.53 Sulfate 11 11 16.2 22 52 75 219 236 TDS 12 12 660.1 1251.75 1966 2194 17318.2 22372

Table 13. Animal contaminated ground water samples that exceed EPA secondary and primary drinking water standards. [MCLs are U.S. EPA Maximum Contaminant Levels for public water supplies; SDWRs are Secondary Drinking Water Regulations that are non-enforceable guidelines regarding cosmetic or aesthetic effects in drinking water; HBSLs are Health-Based Screening Levels developed by the USGS using EPA toxicity data and methods; --, not applicable. All benchmark and guideline values are in milligrams per liter.] Benchmark or guideline Human-health benchmark Non-health guideline Nutrient, major ion, and trace element Wells exceeding Wells exceeding Value Type Value Type benchmarks (Percent) guideline (Percent) Nutrients (mg/L) Nitrate-Nitrite as N 10 MCL 0 ------Trace Elements (mg/L) Arsenic 0.01 MCL NA ------Major ions (mg/L) Aluminum ------0.05 to 0.2 SDWR NA 57 Barium 2 MCL 0 ------

Chloride ------250 SDWR 43 Iron ------0.3 SDWR 18

Manganese 0.3 HBSL 36 0.05 SDWR 55 Strontium 4 HBSL 0 ------

Sulfate ------250 SDWR 0 TDS ------500 SDWR 100

Table 14. Salt contaminated ground water: number of samples, detections, and quantile concentrations. [NA, not analyzed; --, not applicable. All benchmarks and guidelines are in milligrams per liter (mg/L).] Physical property, Concentration at set percentiles Maximum Number of Number of nutrient, major ion, or Concentration or samples detections trace element 10th 25th Median 75th 90th value Physical Property (mg/L)

Alkalinity as CaCO3 29 29 100 198 296 387 427 475 Nutrient (mg/L) Nitrate-Nitrite as N 18 5 0.02 0.13 0.36 1.25 1.4 1.4 Trace Element (mg/L) Arsenic NA NA NA NA NA NA NA NA Major Ions (mg/L) Aluminum NA NA NA NA NA NA NA NA Barium 14 14 0.02 0.03 0.06 0.09 0.16 0.19 58 Bromide 37 34 0.03 0.06 0.12 0.67 1.15 4

Calcium 59 59 4.8 11 67 134 260 470 Chloride 60 60 32.4 57.5 229.5 790 6973 54015 Iron 43 34 0.01 0.01 0.08 3.93 5.3 5.6 Magnesium 59 59 1.2 3.7 15.4 48 66 110 Manganese 45 30 0.001 0.01 0.09 0.39 0.52 0.88 Potassium 59 56 0.3 0.5 2.05 7 15.9 26 Sodium 60 60 24.2 59 113 420.25 3951 35496 Strontium 17 17 0.08 0.11 0.14 0.23 0.55 1.27 Sulfate 59 59 13 18 34 52 150 248 TDS 15 15 275.6 910 6670 12400 12680 12800

Table 15. Salt contaminated ground water samples that exceed EPA secondary and primary drinking water standards. [MCLs are U.S. EPA Maximum Contaminant Levels for public water supplies; SDWRs are Secondary Drinking Water Regulations that are non-enforceable guidelines regarding cosmetic or aesthetic effects in drinking water; HBSLs are Health-Based Screening Levels developed by the USGS using EPA toxicity data and methods; --, not applicable. All benchmark and guideline values are in milligrams per liter.] Benchmark or guideline Human-health benchmark Non-health guideline Nutrient, major ion, and trace element Wells exceeding Wells exceeding Value Type Value Type benchmarks (Percent) guideline (Percent) Nutrients (mg/L) Nitrate-Nitrite as N 10 MCL 0 ------Trace Elements (mg/L) Arsenic 0.01 MCL NA ------Major ions (mg/L) Aluminum ------0.05 to 0.2 SDWR NA

59 Barium 2 MCL 0 ------

Chloride ------250 SDWR 47 Iron ------0.3 SDWR 30

Manganese 0.3 HBSL 20 0.05 SDWR 36 Strontium 4 HBSL 0 ------

Sulfate ------250 SDWR 0 TDS ------500 SDWR 80

Graphical Results for Ground Water and Contaminated Water Groups

Box and Whisker Plots

Box and whisker plots were constructed for the 1980s Lock Haven, 1980s

Catskill, and 2012-2013 ground water samples, as well as Marcellus shale flow-back samples. Examining the box and whisker plots (Figure 9) and associated data table for each group (Table 16) shows that TDS concentrations of the ground water samples are separated from flow-back by more than two orders of magnitude. However, dilute flow- back and ground water mixtures may begin to approach ground water TDS concentrations (Figure 9). In order to test this, a 10% flow-back, 90% ground water mixture was calculated for both Catskill and Lock Haven aquifers. This mixture was calculated by multiplying the mean concentration of flow-back by 0.1 and the mean concentration of ground water by 0.9, then adding the two results to get the mixture concentration (Table 17). Additionally, 5%, 1%, and 0.5% flow-back concentrations were also calculated and plotted on the box and whisker plot. The Catskill box and whisker plot shows that it would take a flow-back concentration of 0.4% for flow-back and ground water mixtures to overlap with the highest Catskill sample. Similarly, the Lock

Haven box and whisker plot would require a flow-back concentration of 0.9% for flow- back and ground water mixtures to overlap with the highest Lock Haven sample. At this concentration, contamination from flow-back might be possible; however, it would also be just as likely to suspect other types of TDS contaminants, such as road salt, animal waste, or septic effluent. For example, the previous section on TDS contaminant ranges

60 showed that animal waste and road salt can more than exceed the maximum TDS concentrations for Catskill and Lock Haven wells (Tables 12 & 14). Samples collected in

2012-2013 in northeastern Pennsylvania have even lower concentrations than the 1980s samples, and don’t even capture the full range of historic TDS variability in the aquifer.

This suggests that total dissolved solids in local ground water in northeastern

Pennsylvania have not been detectably impacted by Marcellus shale flow-back spills or leaks.

Figure 9. Quantile Box and whisker plot of TDS, for Catskill, Lock Haven, NE PA samples, and flow-back.

Table 16. TDS quantile values for Catskill, Lock Haven and NE PA ground water samples and Marcellus flow-back. Catskill Lock Haven Flow-back NE PA Samples Quantile % TDS (mg/L) TDS (mg/L) TDS (mg/L) TDS (mg/L) 100% maximum 874 1,706 358,000 432 90% 373 513 334,200 407 75% 3rd quartile 254 306 230,063 311 50% median 162 246 152,000 232 25% 1st quartile 108 180 93,275 96 10% 68 142 28,874 31 0% minimum 18 70 8,520 12

Table 17. Flow-back and ground water TDS mixture concentrations. 90% Groundwater 95% Groundwater 99% Groundwater 99.5% Groundwater 10% Flow-back 5% Flow-back 1% Flow-back .5% Flow-back Lock Haven 15,946 8,120 1,859 1,076 (mg/L) Catskill 15,871 8,040 1,776 993 (mg/L)

Piper Diagrams

Piper diagrams for the Lock Haven (Figure 10) and Catskill (Figure 11) ground water samples shows that most of the samples plot within the calcium-bicarbonate zone.

The Lock Haven and Catskill mean supports this observation, also plotting in the calcium-bicarbonate zone. Comparing the two-standard-deviation shapes for the two formations, we see that the cation (left triangle), anion (right triangle), and diamond standard deviation shapes are similar and overlap considerably. This shows that the two formations are relatively similar. Piper diagrams also show that the Lock Haven and

Catskill aquifers commonly plot in the calcium-bicarbonate zone, a zone that can be characterized as the region’s ground water fingerprint.

The piper diagram for Marcellus shale flow-back shows that all but one sample plots in the sodium-chloride water zone (Figure 12). The mean point and the two- standard-deviation shape also fall in the sodium-chloride zone. To understand how the plotting position of flow-back fluid might change as it mixes with local ground water, a hypothetical solution of 1% of the mean flow-back chemistry and 99% of the mean Lock

Haven ground water was plotted. Even with this dilute concentration of 1% flow-back and 99% Lock Haven ground water, the hypothetical solution only moves away from the flow-back samples slightly.

Figure 10. Lock Haven Piper Diagram.

Figure 11. Catskill Piper Diagram.

Figure 12. Marcellus shale flow-back Piper Diagram.

The piper diagrams of potential northeastern Pennsylvania contaminants plot in various water zones. Ground water samples contaminated by animal waste mostly plot in the calcium-bicarbonate water zone, which is where the group mean also plots (Figure

13). The septic tank effluent samples seemingly plot all over the piper diagram; however, the group mean is located in the sodium-chloride water zone (Figure 14). This variation in septic tank chemistry may be due to the discharge of water softener salts and other household chemicals into the septic system (Mullaney et al., 2009). Ground water samples contaminated by road salt mostly plot from sodium-chloride waters toward calcium-bicarbonate waters, with the average plotting within the sodium-chloride water zone (Figure 15). This variation among road salt samples is most likely caused by dilution. The dilution of road salt ions increases further from the salt source resulting in lower concentrations, while concentrations closer to the salt source will be less dilute or more concentrated. Each one of these contaminant groups overlaps with one another and the ground water samples, making it difficult to determine if ground water samples were affected by animal waste, septic effluent, or road salt (Figure 16).

Figure 13. Animal Waste Piper Diagram.

Figure 14. Septic tank effluent Piper Diagram.

Figure 15. Road salt Piper Diagram.

Figure 16. Piper Plot of road salt, animal waste, septic effluent, and flow-back 2 standard deviation zones.

The final piper diagram generated was for the 21 ground water samples collected for this study (Figure 17). The 2012-2013 ground water samples plot similarly to both

Lock Haven and Catskill ground water samples. Fourteen samples plot in the calcium- bicarbonate water zone; six samples plot in the sodium-bicarbonate zone; and one sample plots in the calcium-chloride water zone. Although all of these samples fall within the

Catskill and Lock Haven sample range, the one calcium-chloride sample sticks out from the group. This sample (Tioga-8) plots within the range of septic effluent, road salt, and animal waste. It will be discussed further in later sections. Another important thing to notice about the 2012-2013 samples is that none of them trend toward the Marcellus shale flow-back samples. Overall, the piper diagrams show that all of the 2012-2013 samples fall within the range of local ground water; while one sample might be contaminated by road salt, septic effluent or animal waste. No samples appear to have been detectably contaminated with Marcellus flow-back.

Figure 17. 2012-2013 northeastern Pennsylvania Piper Diagram.

Stiff Diagrams

Looking at the ground water Stiff diagrams for Catskill and 2012-2013 samples, the shapes are similar and match the calcium-bicarbonate water zone predicted in the

Piper diagrams (Figure 18). However, the Lock Haven shape differs from the Catskill and has more sodium than calcium, giving it a sodium-calcium-bicarbonate shape. This water zone differs from the zone predicted in the Piper diagram, most likely because the Piper diagram excluded some samples lacking complete cation and anion data. As a result, the

Stiff diagram for Lock Haven ground water is probably more representative of the ground water chemistry than the Piper Diagram results.

Examining the shapes for Marcellus flow-back, animal waste, road salt, and septic effluent, it is evident that each sample has a different shape with different extents (Figure

19). However, comparing these chemical water shapes to their equivalent Piper water zone, they match up perfectly, validating the Piper diagrams.

Stiff Diagram CATIONS IONS 4 3 2 1 0 1 2 3 4

Na+K Cl

Ca HCO3+CO3

Mg SO4

Lock Hav en

Na+K Cl

Ca HCO3+CO3

Mg SO4

Catskill

Na+K Cl

Ca HCO3+CO3

Mg SO4

NE PA Samples

Figure 18. Stiff diagram for Lock Haven, Catskill, and 2011-2012 NE PA samples.

Stiff Diagram CATIONS IONS 3000 2500 2000 1500 1000 500 0 500 1000 1500 2000 2500 3000

Na+K Cl

Ca HCO3+CO3

Mg SO4

Marcellus Flow-back

Stiff Diagram CATIONS IONS 70 60 50 40 30 20 10 0 10 20 30 40 50 60 70

Na+K Cl

Ca HCO3+CO3

Mg SO4

Animal Waste

Na+K Cl

Ca HCO3+CO3

Mg SO4

Road Salt

Na+K Cl

Ca HCO3+CO3

Mg SO4

Septic Ef f luent

Figure 19. Stiff diagram for flow-back, animal waste, salt, and septic effluent.

Using the ground water Stiff diagrams created above, the individual 2012-2013 ground water samples could be compared to either the Lock Haven or Catskill ground water. Examining these samples for similarities to sodium-calcium-bicarbonate Lock

Haven, and calcium-bicarbonate Catskill ground waters, it is important to notice that each sample falls into one of these groups except for sample Tioga-8 (Figure 20). Tioga-8 has calcium-chloride type water, which not only doesn’t match ground water, it also doesn’t match any contaminant. Looking at the cation side for Tioga-8, the shape is similar to

Catskill ground water and animal waste. The anion side is shaped similarly to septic effluent, road salt, and flow-back; however, the magnitude is most similar to septic effluent. It appears that this sample consists of Catskill ground water contaminated by septic effluent.

Stiff Diagram CATIONS IONS 6 5 4 3 2 1 0 1 2 3 4 5 6

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-1

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-2

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-3

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-4

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-5

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-6

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-7

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-8

Figure 20. Stiff diagrams for 2012-2013 northeastern PA samples.

Stiff Diagram CATIONS IONS 6 5 4 3 2 1 0 1 2 3 4 5 6

Na+K Cl

Ca HCO3+CO3

Mg SO4

BR-1

Na+K Cl

Ca HCO3+CO3

Mg SO4

BR-2

Na+K Cl

Ca HCO3+CO3

Mg SO4

BR-3

Na+K Cl

Ca HCO3+CO3

Mg SO4

BR-4

Na+K Cl

Ca HCO3+CO3

Mg SO4

BR-5

Na+K Cl

Ca HCO3+CO3

Mg SO4

BR-6

Na+K Cl

Ca HCO3+CO3

Mg SO4

BR-7

Na+K Cl

Ca HCO3+CO3

Mg SO4

BR-8

Na+K Cl

Ca HCO3+CO3

Mg SO4

BR-9

Na+K Cl

Ca HCO3+CO3

Mg SO4 BR-10 FigureNa+K 20 continued. Stiff diagrams for 2012-2013 northeastern PA samples. Cl Ca HCO3+CO3 Mg SO4 Ly -1

Na+K Cl

Ca HCO3+CO3

Mg 78 SO4

Ly -2

Na+K Cl

Ca HCO3+CO3

Mg SO4

Su-1

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-1

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-2

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-3

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-4

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-5

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-6 Stiff Diagram CATIONS IONS 6 5 4 3 2 1 0 1 2 3 4 5 6

Na+K Cl

Ca HCO3+CO3

Mg SO4

Ly -1

Na+K Cl

Ca HCO3+CO3

Mg SO4

Ly -2

Na+K Cl

Ca HCO3+CO3

Mg SO4 Su-1 FigureNa+K 20 continued. Stiff diagrams for 2012-2013 northeastern PA samples. Cl Ca HCO3+CO3 Mg SO4 Tioga-1

Na+K Cl

Ca HCO3+CO3

Mg SO4 Tioga-2

Na+K Cl Ca HCO3+CO3 Mg SO4 Tioga-3 Na+K Cl Ca HCO3+CO3 Mg SO4

Tioga-4

Na+K Cl

Ca HCO3+CO3

Mg SO4

Tioga-5 Na+K Cl Ca HCO3+CO3 Mg SO4 Tioga-6

Cross-Plot Mixing Model

A Cl/Br vs. Cl cross plot was created for all available 1980s ground water, 2012-

2013 samples, flow-back, animal waste, septic effluent, and road salt samples (Figure

21). The number of data points that could be plotted on the cross-plot was greatly limited by the lack of bromide data for many of the samples. This was especially true for the

Lock Haven and Catskill ground water samples, since the majority of these samples were collected in the early 1980s when most analyses didn’t include bromide. As a result, only fourteen Lock Haven and one Catskill ground water sample were plotted. This lack of data has potentially limited the spread of samples, so in order to predict where additional data might plot, a two-standard-deviation line from the chloride average was created for

1980s ground water and 2012-2013 ground water samples. This line therefore represents where 95% of samples should fall, giving a zone where ground water is likely to plot.

It is clear from the cross-plot diagram that the Marcellus flow-back points plot distinctly from the other groups. In fact, even the flow-back mixing zone plots distinctly from the ground water and other contaminated waters. This mixing zone was calculated from points that represented a 10%, 5%, and 1% flow-back and Lock Haven/Catskill mixture. If 2012-2013 ground water had been contaminated with flow-back, it would be expected that some samples would either plot within or near this mixing zone. However, this trend is not observed for any of the northeastern Pennsylvania samples.

From the 21 2012-2013 ground water samples, only three had detectable levels of bromide (>0.1 mg/L). Of these three samples, the sample with the highest chloride concentration, Tioga-8, plots among the septic effluent and animal waste samples.

Looking at the sample with an intermediate chloride concentration, BR-5, it plots on the edge of the ground water and contaminated samples, making it difficult to distinguish.

The final ground water sample with the lowest chloride concentration, BR-6, clearly plots close to the ground water samples. Based on these samples, we can conclude that sample

BR-6 is similar to ground water, Br-5 is most likely similar to ground water, and Tioga-8 is similar to septic effluent or animal waste. For the remaining 18 samples that did not have detectable levels of bromide, these samples were plotted using half the bromide detection limit (Figure 22). Although this method is generally considered to be less precise (Helsel, 2006), these values are not being used for quantitative statistical analysis, and are therefore acceptable. These values are being used to see where data might plot.

Looking at these points it seems as though six additional samples, which include BR-1,

Tioga-2, BR-2, Ly-2, BR-3, and BR-7 have a chance of being contaminated by septic effluent, animal waste, or road salt. These results are interesting; however, this study makes no claim that each of these samples are definitively contaminated by septic effluent or road salt.

Flow-back Avg

Marcellus Flow-back 10,000 Road Salt Avg Road Salt Road Salt

Septic Effluent Avg Salt , Septic, & 1,000 Animal Waste Zone Septic Effluent Animal Waste Avg

Animal Waste

Flow-back 1980s Lock Haven Avg Cl/Br

82 100 Mixing Zone Marcellus 1980s Lock Haven Flow-back 1980s Catskill

2012-2013 GW Avg

Ground Water 2012-2013 Samples 10

1 1 10 100 1,000 10,000 100,000 Chloride (mg/L)

Figure 21. Cl/Br vs. Cl cross-plot with all data points and group averages, along with ground water 2 S.D. lines marked with the mean, and a mark on the chloride axis indicating the secondary maximum contaminant level (250 mg/L).

Flow-back Avg

Marcellus Flow-back 10,000 Road Salt Avg

Road Salt Road Salt

Septic Effluent Avg Salt , Septic, & 1,000 Animal Waste Zone Septic Effluent Animal Waste Avg

Animal Waste

Flow-back 1980s Lock Haven Avg Cl/Br

83 Mixing Zone 100 Marcellus 1980s Lock Haven Flow-back 1980s Catskill

2012-2013 GW Avg

Ground Water 2012-2013 Samples 10

1 1 10 100 1,000 10,000 100,000 Chloride (mg/L)

Figure 22. Cl/Br vs. Cl cross-plot, with all 2012-2013 samples plotted using half the detection level for bromide.

Statistical Results

Analysis of Variance

The ANOVA test between 1980s Catskill and Lock Haven ground water was completed in JMP 9, at a 5% level of significance. Examining the ANOVA tables for each ion, except bromide, the results varied. Comparing the F-ratio to the critical F value for all 15 different ions, the results show that calcium, magnesium, sodium, alkalinity, sulfate, and nitrate-nitrite as N have an F-ratio larger than the critical F value (Table 18).

This means that for these six elements, the null hypothesis that the average values are equal can be rejected. Instead, the alternative hypothesis that the means differ is accepted.

The remaining nine elements of chloride, potassium, TDS, iron, barium, strontium, arsenic, aluminum, and manganese had F-ratios that were less than the critical F value.

Therefore, the null hypothesis that the means are equal can be accepted. Overall, these results show that nine of the ions are statistically similar, while six ions are not similar.

Although the majority of ions are similar, 40% of ions have statistically significant differences in concentration. Because of this, both ground water aquifers will be kept separate, as much as the dataset allows.

Table 18. ANOVA ion comparison table, using log normalized data. Means

Catskill Lock Haven F Ratio Prob > F Fcrit Ca 1.53 1.67 23.46 <.0001 3.84 Mg 1.18 1.28 42.05 <.0001 3.84 Na 1.41 1.51 3.97 0.0478 3.84 K 1.05 1.06 1.69 0.1945 3.84

HCO3 1.97 2.17 17.18 <.0001 3.84 Cl 1.33 1.38 1.13 0.2894 3.84

SO4 1.33 1.47 21.52 <.0001 3.84 TDS 2.18 2.24 1.54 0.2169 3.84 Al 1.01 1.01 2.16 0.1434 3.84 Ba 1.02 1.03 0.48 0.4897 4.03 Fe 1.02 1.03 0.53 0.4654 3.84 Sr 1.01 1.02 0.21 0.6474 3.95 As 1.00 1.00 1.59 0.2134 4.08 Mn 1.00 1.01 0.81 0.3692 3.84

NO3-NO2 1.04 1.02 9.09 0.0030 3.84

Discriminant Analysis

In order to compare the results from the Cl/Br vs. chloride cross-plot, the initial discriminant analysis used the variables of chloride, bromide, and Cl/Br. For this analysis, bromide data was inserted at half the detection level for those 2012-2013 samples with bromide concentrations below the detection limit. Also, the only Catskill sample which had a bromide analysis was combined with the Lock Haven samples to reduce the number of groups. Additionally, in order to avoid unwanted group interference from the 2012-2013 ground water samples, the discriminant analysis was run without this group. This allowed the 1980s ground water, animal waste, septic effluent, road salt, and

Marcellus flow-back samples to be properly classified into their most likely groups without influence from unidentified 2012-2013 ground water samples.

The initial discriminant analysis correctly classified only 3 out of 11 animal waste samples (Table 19). For the septic effluent and road salt samples, both had fairly good classification rates. The discriminant analysis correctly classified 20 out of 29 septic effluent samples, and 24 out of 34 road salt samples. The only samples classified as flow- back, were the flow-back samples, with 16 out of 18 samples correctly classified. Finally,

12 out of 15 1980s ground water samples were correctly identified. Overall, this initial discriminant analysis misclassified 30% of the known samples.

Examining the classification results for the 2012-2013 ground water samples, 10 of the 2012-2013 samples were classified as ground water, 4 were classified as animal waste affected waters, and 7 were classified as septic effluent affected waters (Table 19).

Interestingly those samples classified as contaminated included BR-1, BR-2, BR-3, BR-7,

Ly-2, Tioga-2, and Tioga-8 from septic effluent, and four other samples contaminated with animal waste. These listed samples are the same samples identified as contaminated in the cross-plot. However, because of the uncertainty of bromide in non-detect data, only

Tioga-8 can be classified as contaminated with a high degree of certainty. Also, looking at the group classification probabilities for each of the 2012-2013 ground water samples, none have a classification probability greater than 70% (Table 20). For example, the

2012-2013 ground water samples that were classified as ground water had a min, mean, and max probability of 38%, 56%, and 70%. This shows that many of the ground water samples are not strongly classified, and indicates that the variables of Cl, Br, and Cl/Br may not have been the best option.

In order to verify the results from the first discriminant analyses, another discriminant analysis was conducted using the variables of Ca, Mg, Na, Cl, Cl/SO4,

Ca/SO4, HCO3/Mg, and HCO3/Cl. This discriminant analysis correctly classified 10 out of 11 animal waste samples, and 26 out of 41 septic effluent samples (Table 21). The road salt samples were correctly classified 20 out of 29 samples. Three of the flow-back samples were correctly identified as flow-back, while one sample was identified as road salt. The one flow-back sample identified as road salt was a sample that had relatively low chloride concentrations more similar to elevated road salt samples. Finally, 133 out of 150 ground water samples were correctly classified. Overall, this second discriminant analysis misclassified only 18% of the known samples.

The results from the second discriminant analysis showed that eighteen of the

2012-2013 samples were identified as ground water, while two samples were classified as

87 septic effluent (Table 21). One sample, Br-5 could not be assigned a group because it had a non-detect value for sulfate. The contaminated samples were identified as Tioga-2, and

Tioga-8 (Table 22). Looking at the classification probabilities for the 2012-2013 ground water samples, it is noticeable that the separation between the ground water and contaminated groups is much greater than the first analysis (Table 22). For example, the

2012-2013 ground water samples that were classified as ground water have a much higher minimum, mean, and maximum probability of 53%, 91%, and 99%. This indicates that the second analysis does a much better job at separating the groups, which results in more confidence in group assignment.

Overall, discriminant analysis is a useful method to classify the 2012-2013 ground water samples into their most likely group. This analysis has provided additional support to the previous methods results, in that none of the ground water samples appear to have been impacted from Marcellus shale flow-back. Additionally, discriminant analysis has provided support that several samples are likely to be contaminated with either septic effluent or animal waste.

Table 19. Discriminant analysis 1, classification result table with ground water as one group, using Cl, Br, and Cl/Br ratios. Animal Septic Road Marcellus Ground N Waste Effluent Salt Flow-back Water Animal Waste 11 27% 46% 0% 0% 27% Septic Effluent 29 7% 69% 21% 0% 3% Road Salt 34 0% 26% 71% 0% 3% Marcellus Flow-back 18 0% 0% 0% 89% 11% Ground Water 15 20% 0% 0% 0% 80% 2012-2013 Samples 21 19% 33% 0% 0% 48% Percentage of Samples Misclassified 30%

Table 20. 2012-2013 ground water samples, and their designated probability of falling into a certain group for discriminant analysis 1. Probabilities to Each Group Animal Waste Septic Road Salt Flow-back Ground Water BR-1 0.100 0.600 0.266 0.000 0.034 BR-2 0.211 0.578 0.104 0.000 0.108 BR-3 0.274 0.495 0.058 0.000 0.172 BR-4 0.328 0.024 0.000 0.000 0.647 BR-5 0.457 0.180 0.023 0.000 0.340 BR-6 0.432 0.150 0.010 0.000 0.409 BR-7 0.302 0.447 0.043 0.000 0.208 BR-8 0.339 0.031 0.001 0.000 0.629 BR-9 0.290 0.010 0.000 0.000 0.700 BR-10 0.350 0.334 0.022 0.000 0.294 Ly-1 0.383 0.202 0.008 0.000 0.407 Ly-2 0.261 0.517 0.066 0.000 0.157 Su-1 0.340 0.032 0.001 0.000 0.627 Tioga-1 0.347 0.038 0.001 0.000 0.614 Tioga-2 0.155 0.613 0.166 0.000 0.065 Tioga-3 0.328 0.024 0.000 0.000 0.648 Tioga-4 0.385 0.119 0.004 0.000 0.492 Tioga-5 0.368 0.278 0.015 0.000 0.339 Tioga-6 0.380 0.223 0.010 0.000 0.387 Tioga-7 0.386 0.135 0.004 0.000 0.475 Tioga-8 0.211 0.505 0.200 0.000 0.084

Table 21. Discriminant analysis 2, using the following ions and ionic ratios: Ca, Mg, Na, Cl, Cl/SO4, Ca/SO4, HCO3/Mg, and HCO3/Cl. Discriminant Analysis Animal Septic Road Marcellus Ground N 2 Waste Effluent Salt Flow-back Water Animal Waste 11 91% 0% 0% 0% 9% Septic Effluent 41 10% 63% 12% 0% 15% Road Salt 29 14% 10% 69% 0% 7% Marcellus Flow-back 4 0% 0% 25% 75% 0% Ground Water 150 0% 11% 0% 0% 89% 2012-2013 Samples 20 0% 10% 0% 0% 90%

Table 22. 2012-2013 Ground Water Samples, and their designated probability of falling into a certain group for discriminant analysis 2. Probabilities to Each Group Animal Waste Septic Road Salt Flow-back Ground Water BR-1 0.000 0.027 0.000 0.000 0.973 BR-2 0.001 0.311 0.001 0.000 0.687 BR-3 0.000 0.099 0.000 0.000 0.901 BR-4 0.000 0.011 0.000 0.000 0.989 BR-5 ------BR-6 0.000 0.026 0.000 0.000 0.974 BR-7 0.000 0.166 0.000 0.000 0.833 BR-8 0.000 0.008 0.000 0.000 0.992 BR-9 0.000 0.004 0.000 0.000 0.996 BR-10 0.000 0.070 0.000 0.000 0.930 Ly-1 0.000 0.046 0.000 0.000 0.954 Ly-2 0.000 0.009 0.000 0.000 0.991 Su-1 0.000 0.003 0.000 0.000 0.997 Tioga-1 0.000 0.004 0.000 0.000 0.996 Tioga-2 0.000 0.582 0.004 0.000 0.414 Tioga-3 0.000 0.004 0.000 0.000 0.996 Tioga-4 0.000 0.016 0.000 0.000 0.984 Tioga-5 0.006 0.369 0.001 0.000 0.624 Tioga-6 0.031 0.435 0.000 0.000 0.533 Tioga-7 0.000 0.040 0.000 0.000 0.960 Tioga-8 0.000 0.599 0.061 0.000 0.340

DISCUSSION

Interpretations

Through the use of various graphical and statistical methods, this project determined that Marcellus shale flow-back has not detectibly impacted the 21 ground water wells that were sampled for this project. However, these methods do provide evidence for contamination by animal waste, septic effluent, or road salt for some of the

2012-2013 ground water samples.

The descriptive statistics for the ground water and contaminant groups helped to identify which ions were commonly exceeded. These statistics also helped identify major ion concentration ranges for each group. Based on the descriptive statistics, it was determined that the 1980s Catskill and Lock Haven ground water samples commonly exceed EPA secondary water standards for iron, manganese, and aluminum. For the septic effluent, animal waste, road salt, and flow-back contaminant groups, some of the commonly exceeded EPA secondary water standards are TDS, iron, manganese, and chloride. Perhaps the most characteristic ion is chloride, which is elevated in 16% of septic impacted samples, 43% of animal waste affected samples, 47% of road salt affected samples, and 100% of flow-back samples. If local ground water in northeastern

Pennsylvania had been impacted from flow-back spills, then it would have been expected to find elevated chloride concentrations in water wells closer to Marcellus wells.

However, looking at the 2012-2013 ground water chloride data and the corresponding distance to the nearest Marcellus well there is no discernable trend (Figure 23). None of the 2012-2013 samples even exceed the EPA secondary contaminant level for chloride which is set at 250 mg/L.

Box and whisker plots identified that the TDS concentrations for 2012-2013 ground water samples plot similarly to samples from the Catskill and Lock Haven aquifers collected in the 1980s. The 2012-2013 samples were also two orders of magnitude smaller than the flow-back fluid TDS concentration. Box and whisker plots also showed that the 2012-2013 samples did not overlap with any of the calculated flow- back and ground water mixtures. This method provided a nice first look at where the data plots, and whether contamination from flow-back fluid is likely or not.

Piper diagrams were also effective at distinguishing between ground water and flow-back. The Lock Haven, Catskill, and 2012-2013 samples predominantly plotted in the calcium-bicarbonate zone, while the flow-back plots on the top line of the sodium- chloride group. None of the 2012-2013 samples came close to the flow-back samples; however, one sample, Tioga-8, plotted away from the group and may be contaminated by road salt, septic effluent, or animal waste. Piper diagrams were not effective at distinguishing between road salt, animal waste, and septic tank effluent, due to sample overlap. These contaminated samples also overlapped with the ground water samples making it impossible to distinguish between the groups.

Stiff diagrams were an effective method for validating and double checking the

Piper diagram results. This method confirmed the water type for each group except the

Lock Haven samples. The Lock Haven Piper classification may have been biased since the Piper diagram only plotted samples with complete data sets, which excluded samples without complete cation and anion sets. Stiff diagrams avoided this problem by using average values for cations and anions, and allowed more samples to be represented. Stiff diagrams were also a valuable tool for comparing each individual 2012-2013 sample to the ground water and contaminant groups. Using this method one of the 2012-2013 thesis samples, Tioga-8, had an uncategorized water type. This sample was identified as septic effluent contaminated Catskill ground water, based on the cation shape that was similar to

Catskill ground water and the anion shape that was similar to septic effluent.

The Cl/Br vs. Cl cross-plot was an extremely powerful method for separating

1980s Lock Haven and Catskill ground water from Marcellus flow-back and contaminated samples. However, the cross-plot was not very good at separating the septic, animal waste, and road salt contaminant groups. This method was also limited to data with bromide values, which consequently limited the number of ground water points.

Plotting the 2012-2013 samples showed that one sample, Tioga-8, was almost certainly impacted from either septic effluent or animal waste. None of the 2012-2013 samples trended toward the mixing zone between ground water and flow-back fluid.

The use of ANOVA provided useful insight into the variability of the two 1980s ground water aquifers. This test determined that the 1980s Lock Haven and Catskill ground water groups are statistically different, and therefore should be kept separate as much as possible when making comparisons.

Discriminant analysis was successful at classifying which group the 2012-2013 samples most likely belong to. The first discriminant analysis helped verify the results from the Cl vs. Cl/Br cross-plot, and identified the same seven potentially contaminated samples, including Tioga-8. One problem with this analysis was the lack of bromide data for many samples, which limited the number of samples that could be used. The second discriminant analysis used the variables of Ca, Mg, Na, Cl, Cl/SO4, Ca/SO4, HCO3/Mg, and HCO3/Cl, and was much better at classifying the ground water and contaminant groups. This analysis only misclassified 18% of the samples, which was much better than

30% for the first analysis. This second analysis also identified Tioga-8 and Tioga-2 as contaminated from septic effluent, but none were identified as flow-back.

Throughout each of these graphical and statistical methods, one of the 2012-2013 samples was consistently identified as being contaminated from septic effluent or animal waste. This sample, Tioga-8, was located on a dairy farm where animal waste is present and plentiful. Examining this well’s chemistry also showed that this sample had a nitrate- nitrite as N concentration of 14 mg/L, which was the only water sample with nitrate- nitrite above the EPA maximum contaminant level (Appendix 4). However, the well owner never considered contamination from animal waste and instead blamed their water issues on a Marcellus gas well 3,300 feet (1,006 meters) away. They even claimed that their supposedly Marcellus contaminated water had killed one of their calves. This example shows that many rural well owners seem to be unaware of the potential threats that are in their own back yard, such as septic tanks, animal waste, or fertilizers.

100 Tioga-8 90

80 BR-1

60 BR-5 50 Tioga-2

40 BR-2

Chloride (mg/L) Chloride 30 BR-6 Ly-2 BR-3 20 BR-7 BR-10 10 Tioga-5 Tioga-6 Ly-1 Tioga-7 Tioga-4 BR-8 BR-9 Su-1 0 Tioga-3 BR-4 Tioga-1 100 1,000 10,000 100,000

Distance from Marcellus Well (ft)

Figure 23. Chloride concentration of 2012-2013 ground water samples with distance to nearest gas well.

Limitations

Although the graphical and statistical methods used in this study could characterize the 2012-2013 ground water samples into one of the historical or contaminated ground water sources, it might have been easier had there not been numerous limitations on the analyzed data. One of the largest data limitations on this study was the access to only major ions, nutrients, and physical properties for the historical and contaminated ground water samples. This limitation made it impossible to compare historical and contaminated ground water to some of the trace elements and chemicals that are characteristic of flow-back fluid, like bromide, alcohols, ethylene glycol, oil and grease, radiologicals, and isotopes (Frac Focus, 2013).

Another limitation that was encountered while completing this project was the lack of Marcellus shale flow-back data. Even though a file review was conducted at the

Pennsylvania DEP, the final sample size was limited by the lack of complete Form 26Rs.

For example, after reviewing several hundred files, it was noticed that most energy companies only submitted one Form 26R with chemistry data. This, represented one well, but the companies claimed that it was representative of all flow-back from multiple well locations.

Another limitation on this study was the lack of published contaminated ground water data for northeastern Pennsylvania. Although it was assumed that contaminated data from other regions were similar to northeastern Pennsylvania contaminated data, it would have added more confidence to the study if local data had been used. A final limitation to this study was the collection of only one sample from a single point in time

96 for the 2012-2013 samples. It would have been ideal if two or more samples could have been collected from each site to assure the first sample was representative of each location’s ground water.

Future Work/Recommendations

In order to make future contaminant hydrogeology research in northeastern

Pennsylvania more robust, several specific projects could be conducted. One of these projects could involve the characterization of local contaminant sources. The study of common rural contaminants in northeastern Pennsylvania, like septic effluent, animal waste, fertilizers, and road salt would be valuable to anyone interested in identifying potential contaminants in the region. Another project could include the collection of a detailed and regionally extensive Marcellus flow-back dataset. The collection of a detailed flow-back dataset could prove useful whenever there is a flow-back spill or leak.

This data would give researchers, the government, and energy companies an average concentration or concentration range for the flow-back, from which they could calculate the spill’s environmental impact. A third project that could benefit future ground water studies in the region would be to collaborate with energy companies to obtain their pre- drill ground water data. All of the energy companies have collected pre-drill ground water samples from wells within 2,500 feet (762 meters) of each gas well, so there is a tremendous amount of current ground water data owned by these companies. If these data were made available, it could greatly increase the understanding of ground water variability by location and geologic formation in northeastern Pennsylvania.

CONCLUSION

Overall, the use of graphical and statistical methods has shown that it is possible to use major cations and anions to identify whether flow-back has contaminated local ground water in northeastern Pennsylvania. In fact, these methods have overwhelmingly shown that the 2012-2013 ground water samples have not been detectibly impacted from flow-back fluid spills or leaks. This, however, is not to say that flow-back fluids have no potential to contaminate ground water, because it has been documented that flow-back spills and leaks have occurred in the region (PADEP fines Talisman, 2010; PADEP fines

Chesapeake, 2012; PADEP fines Terraqua, 2012). This study simply finds that no such contamination has been detected at the 21 residential wells sampled for this project.

This study also discovered that most of the complaints homeowners had with their water quality was the result of natural geochemical conditions in the aquifer, while at least 1 well, and perhaps several well complaints were caused by either septic effluent or animal waste. For example, from the 21 ground water wells tested, all ion concentrations were within the range of the 1980s ground water. Also, when these ions did exceed the

EPA primary or secondary contaminant levels, the most common exceedances were typically manganese or iron, similar to the natural hydrochemistry of the Catskill and

Lock Haven aquifers. Some of the less common EPA exceedances for these samples were arsenic and aluminum, which are also common natural ground water contaminants. Only one sample had an exceedance for nitrate-nitrite as N, which was not common in local

98 ground water. This sample is believed to have been contaminated from animal waste or septic effluent. In conclusion, this study has identified local ground water pollution in northeastern Pennsylvania; however, there is no evidence in this study that contamination is from Marcellus flow-back.

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109

APPENDIX 1

Historical Ground Water Data

110

Nitrite Nitrite

Iron

as N as

TDS

Sulfate

Barium

Arsenic

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Magnesium Nitrate Br-126 42 14.3 25 1.7 200 5 10 276 0.04 0.03 ND 0.08 0.022 Br-127 52.5 16.7 28 2.32 196 47 65 338 0.02 0.42 ND 0.06 0.022 Br-130 32.1 9.6 11.7 1.74 136 1 10 196 0.02 0.08 ND 0.02 0.322 Br-132 51 11.2 44 1.04 210 5 10 330 0.05 1.04 ND 0.14 0.022 Br-134 23.4 3.9 3.6 0.38 44 5 15 300 0.06 0.11 ND 0.01 1.462 Br-152 65.5 12.1 21.6 0.78 132 44 15 370 0.07 0.06 ND 0.1 4.404 Br-176 38.7 8 11 1 130 3 5 144 0.06 0.07 ND 0.05 0.104 Br-178 24.7 4.9 9.7 1.12 90 3 5 106 0.03 0.09 ND 0.02 1.382 Br-180 47.9 10.4 4.9 1.28 156 3 5 156 0.02 0.05 ND 0.01 0.182

111 Br-184 38.7 6.8 5.8 1.36 100 6 10 132 0.03 0.05 ND 0.01 2.162

Br-186 37.7 8.9 9.6 0.98 132 5 5 150 0.06 0.09 ND 0.31 0.022 Br-202 25.2 8.7 115 3.6 408 16 0.2 0.6 0.44 1.1 ND 0.04 Br-202 22.3 7.9 271 2.8 216 359 ND 760 0.04 0.56 0.19 1.1 ND 0.05 0.022 Br-203 75.8 11.5 10 1.4 172 10 40 108 0.03 0.16 ND 0.02 4.402 Br-204 36.6 9.2 48.4 3.05 228 10 ND 246 0.06 0.1 ND 0.03 0.204 Br-205 31.1 7.2 156 3.9 185 14 ND 1.6 0.19 1.9 ND 0.07 Br-205 20.6 4.6 156 3.38 184 206 ND 238 0.06 1.62 0.15 1.9 0.0092 0.04 0.022 Br-209 115 20 532 7.9 1080 10 ND 17.2 0.28 14 ND 0.13 Br-238 16.4 3.6 400 3 539 ND ND 0.9 0.03 0.65 ND 0.02 Br-238 12 2.9 245 1.66 240 234 5 664 0.07 0.89 0.2 0.65 ND 0.03 0.022 Br-239 33.7 6.6 32.3 0.9 146 21 ND 216 0.05 0.9 ND 0.23 0.022 Br-242 42.4 10.3 27 1.04 184 2 20 260 0.06 0.77 ND 0.68 0.022 Br-247 38.5 11.6 15.6 2.88 152 3 15 230 0.12 0.21 ND 0.05 1.622

111

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Br-269 42.1 13.2 58.4 1.84 210 10 35 296 0.12 1.28 ND 0.09 0.022 Br-270 39.9 12.2 13.2 2.28 160 1 10 186 0.24 0.54 ND 0.03 0.222 Br-273 50.6 15.6 6.6 2.72 162 2 25 216 1.31 0.04 ND ND 0.022 Br-274 29.3 9.9 75 6.84 254 2 10 266 0.37 0.14 ND 0.05 0.022 Br-286 35 12.2 8.3 2.4 120 5 15 164 0.25 1.06 ND 0.47 0.122 Br-302 66.7 10.3 6.4 1.8 154 29 20 298 0.34 0.01 ND 0.42 0.022 Br-303 61.2 10.5 11 1.76 158 14 20 246 0.11 0.98 ND 0.25 0.022 Br-316 86.7 27.1 60.6 1.88 288 4 115 512 0.2 1.39 ND 2.63 0.028 Br-318 57 12.6 16.1 1.64 180 2 30 266 ND 15.91 0.009 0.41 0.022

112 Br-329 18 4.9 79.7 2.32 210 2 15 288 0.88 1.73 ND 0.05 0.022

Br-344 31.3 8.7 9.2 2.24 110 3 15 138 0.08 0.15 ND 0.11 0.042 Br-346 66.2 18.9 11.8 3.56 210 4 30 270 0.06 0.04 ND 0.03 0.854 Br-353 75.2 23.8 42.9 3.4 346 2 10 386 0.09 3.43 ND 0.42 0.042 Br-357 26.8 4.5 24 2.24 110 14 10 162 0.09 0.82 0.025 0.24 0.042 Br-362 54.7 12.7 52.6 5.76 254 3 20 304 0.13 0.06 ND 0.04 0.042 Br-376 43.6 10 21.9 2.88 172 4 10 202 0.14 0.23 ND 0.14 0.022 Br-377 45.4 10.6 37.9 2.88 208 4 10 224 0.15 0.69 0.0218 0.05 0.022 Br-378 34.4 10.2 37.8 3.88 170 5 15 202 0.24 0.194 0.1 1.58 ND 0.01 0.184 Br-428 82.3 35.3 50.8 3.4 216 4 210 612 0.46 0.67 ND 0.2 0.022 Br-435 71.5 41.1 14.1 2.8 5 75 0.5 ND 0.13 Br-441 42.3 13.1 22.5 1.92 162 20 15 222 0.22 2.42 ND 2.12 0.022 Br-448 31.4 10.1 6.1 2.6 104 5 15 162 0.09 0.56 ND 0.38 0.022 Br-476 12.9 2.7 142.5 3.64 258 28 85 470 0.37 0.5 ND 0.02 0.042 Br-489 66.4 6.5 9.9 2.84 174 4 50 318 0.07 0.1 ND ND 0.992

112

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Br-496 25.3 9.1 7.4 1.68 70 16 15 186 ND 0.4 ND 0.61 1.424 Br-503 54.5 19.3 22.6 2.76 212 2 25 264 0.12 0.31 ND 0.36 0.024 Br-510 55.4 15.9 9.8 3.68 178 5 20 226 0.34 0.22 ND 0.06 0.564 Br-552 59 11.8 7.4 1.2 16 28 ND 0.04 ND ND ND Br-604 50.7 8.8 6.9 1.5 4 20 0.2 0.12 0.21 ND 0.18 Br-606 0.5 0.1 50.1 0.4 3 30 ND 0.03 ND ND ND Br-612 94.5 12.9 43.1 3.2 5 35 0.04 0.09 ND ND Br-620 45.8 8.5 12.2 1.8 14 15 0.2 0.24 0.55 0.011 0.25 Br-621 44.7 12.1 43.2 0.8 15 18 ND 0.3 2.5 0.52 0.026 0.69 113 Br-622 29.5 7.4 3.2 1.2 19 20 0.37 0.11 ND ND Br-627 40.4 7.6 32.4 1 10 0.1 ND 0.11 ND ND Br-630 85.8 19.9 18 2.2 3 40 0.2 0.25 0.45 ND 0.41 Br-632 34.8 6.9 7.8 1.1 21 10 0.3 1.71 0.42 ND 0.22 Br-633 62.1 12.3 26.3 1.4 35 37 0.1 ND 0.22 ND ND Br-634 70.6 12.1 33.1 1.2 121 30 0.4 0.3 3.43 0.13 ND 0.12 Br-637 48.5 12.4 32.9 0.9 10 ND 0.95 0.46 ND 0.14 Br-639 46.2 10.4 38.1 1.5 182 ND 57 256 ND ND 0.23 0.92 ND 0.2 Br-643 33.1 7.5 10 1.9 9 18 ND ND 0.1 0.06 ND ND Br-648 38.2 8.1 6.1 0.7 4 15 0.1 0.11 0.04 ND 0.01 Br-650 55.7 10 8.8 0.9 33 25 0.1 0.1 0.24 0.05 ND 0.01 Br-651 13.8 3.5 89 1.1 13 25 0.1 ND 0.21 0.18 ND 0.13 Br-652 52.8 9.9 8.3 0.8 28 25 0.08 0.05 ND 0.01 Br-657 25.8 5.3 2.1 1 20 ND ND 0.34 0.04 ND ND Br-659 26 3.8 32.7 0.8 10 0.2 ND 1.63 0.03 ND ND

113

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Br-663 26 6.7 7.1 0.9 20 ND ND ND 0.08 ND 1.03 Br-664 50.1 11.4 103 1.2 224 10 0.6 0.69 0.34 ND 0.72 Br-666 15.6 4.2 6.1 0.6 2 25 ND 0.05 0.02 ND 0.02 Br-672 8.2 2.4 165 1.1 292 132 40 471 0.2 0.2 0.07 0.33 ND 0.05 Br-673 47.5 10.3 11.2 1 10 ND 0.13 0.1 ND ND Br-677 30.1 4.5 16.8 0.5 3 21 ND ND 0.69 0.22 ND 0.08 Br-684 39 7 3.9 1.1 6 30 0.6 1.79 0.06 ND 0.08 Br-686 32.1 5.4 10.8 1.4 2 20 1.6 0.2 2.3 0.25 0.007 0.18 Br-687 16 3.5 3.4 1.3 1 21 ND ND ND 0.11 ND ND

114 Br-689 28.3 6.4 56.7 0.9 37 17 ND ND 0.14 0.06 ND 0.3 Br-691 33.3 6.1 60.5 0.4 37 14 ND ND 0.77 0.16 ND 0.26 Br-692 31.9 5.8 4.9 0.6 88 6 25 168 0.06 0.2 0.24 0.12 ND 0.08 Br-694 30.5 5.5 4.2 0.8 5 27 0.1 0.41 0.1 ND 0.08 Br-695 39 8.2 90 2 125 11 ND 3.9 2.45 0.14 0.067 0.08 Br-697 13.4 2.3 5.2 0.7 8 23 ND ND 0.26 0.16 ND ND Br-700 27.8 5.7 16.3 0.8 104 6 25 172 0.05 0.42 0.24 0.29 ND 0.07 Br-703 56.3 15.3 60.5 1.3 3 77 ND 1.5 0.92 ND 0.53 Br-705 40.3 8.6 7.5 1.1 6 29 ND ND ND 0.19 ND ND Br-707 48.6 12.9 8.6 1.3 2 29 ND ND 0.6 0.11 ND 0.35 Br-710 20.4 4.5 19 0.6 102 7 10 144 0.05 0.46 0.27 0.26 ND 0.17 Br-713 33.3 10.9 252 2.3 336 22 ND 1.9 3.55 0.82 0.023 0.44 Br-715 59.9 16.4 18.1 1.4 2 43 ND ND 0.25 0.18 ND ND Br-723 55.4 4.7 5.2 1.1 13 26 ND ND 0.2 0.16 ND ND Br-726 32.8 5.8 29.2 0.7 40 25 0.1 0.1 0.66 0.06 ND 0.08

114

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Br-732 21.1 6.1 8.1 3.2 15 21 0.1 11.2 0.02 ND 0.07 Br-747 95.2 12.2 23 1.7 71 39 ND 0.1 0.01 ND ND ND Br-752 24.5 6 211 3.1 319 11 0.1 1 0.33 0.98 ND 0.08 Br-757 36.4 8.1 15.5 0.7 4 18 ND ND ND 0.09 ND ND Br-764 54.6 12.4 11.5 1 2 26 ND 0.6 0.56 0.48 ND 0.12 Br-765 56.5 12.6 14.1 1.4 12 37 ND 0.2 0.46 0.67 0.036 0.24 Br-766 40.5 9.2 8.2 1.1 90 11 50 230 0.2 0.09 0.13 0.08 ND ND Br-768 199 39.3 86 1.8 30 ND 0.2 0.38 0.23 ND 0.32 Br-779 48.1 11.1 8 0.9 10 50 ND 0.5 1.74 0.16 0.004 0.18

115 Br-806 14.3 4.3 4.6 0.4 3 25 0.1 ND 0.52 0.07 ND 0.56

Br-807 21.4 7 8.8 0.8 11 33 0.1 ND 0.24 0.11 ND 0.68 Br-854 0.117 Br-855 0.039 Ly-510 14.4 4.2 5.8 0.34 42 3 5 104 0.13 0.04 ND 0.01 2.022 Ly-592 1.6 4 19.8 0.6 58 1 8 86 0.12 0.07 ND 0.02 0.14 Ly-594 0.6 0.3 90.5 0.24 186 2 6 200 0.11 0.13 ND 0.01 ND Ly-597 9.6 3.2 24 0.98 86 2 7 134 0.09 0.04 0.0051 0.02 0.12 Ly-600 20.8 7 6.1 0.38 84 1 11 144 0.06 0.07 0.0062 0.03 0.34 Ly-641 25.6 10.3 7.6 0.6 110 2 10 144 0.09 0.1 ND 0.03 0.18 Ly-653 14.4 4.4 25.3 0.44 82 11 17 174 0.05 0.43 ND 0.14 ND Ly-656 2.2 1.3 94.6 0.28 168 25 7 264 0.07 0.04 ND 0.02 ND Su-126 25.4 7.7 12.7 0.72 112 3 6 158 0.07 0.11 ND 0.01 0.256 Su-129 10.5 1.5 1.9 1.04 19 5 10 70 0.02 0.68 ND 0.04 1.002 Ti-100 64 8 9.9 1.5 135 43 22 0.23 0.4 0.65 0.45 NA 0.002 0.33

115

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Ti-101 3.1 7.6 0.2 Ti-101 2.6 7.5 0.2 Ti-102 2.8 14 0.3 Ti-102 2.7 13 0.2 Ti-103 6 26 0.2 Ti-103 6.1 24 0.2 Ti-105 13 33 0.5 Ti-105 12 31 0.2 Ti-108 7.4 12 6.7 1.9 76 2.3 1.6 0.02 0.01 0.03 0.009 0.2 0.001 0.07

116 Ti-108 1.7 ND 0.2 Ti-109 3.4 14 0.4 Ti-109 4.7 11 0.1 Ti-110 18 3 0.4 Ti-110 18 1 0.2 Ti-182 50.9 8.6 7.9 1.72 120 12 30 286 0.09 0.09 ND 0.09 2.424 Ti-188 58.7 25.9 20.1 2.54 254 3 40 356 0.09 0.69 ND 0.11 0.022 Ti-191 25.4 4.4 5.9 0.9 72 13 31 138 0.09 7.91 ND 0.1 0.022 Ti-195 42.6 6.2 6.6 1.72 128 6 30 180 0.06 0.09 ND 0.01 1.642 Ti-200 60.8 32 9.7 2.32 276 3 55 350 0.1 0.07 ND 0.03 0.122 Ti-202 4.5 0.7 176 0.22 224 132 20 514 0.08 0.09 ND 0.02 0.9 Ti-229 31.6 12.9 8 1.78 144 1 5 156 0.07 0.12 ND 0.02 0.084 Ti-234 30.7 12.4 92 2.52 194 66 36 328 0.08 0.17 ND 0.03 0.042 Ti-246 31 12.2 77 2.24 232 40 5 310 0.09 0.67 ND 0.14 0.022 Ti-248 50.8 14.9 9.2 2.56 186 4 25 250 0.07 0.17 ND 0.17 0.042

116

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Ti-252 30.4 6.9 66 2.22 202 25 ND 260 0.06 0.72 0.046 0.05 0.022 Ti-253 38.7 8.4 69 2.6 228 42 5 300 0.04 0.68 0.0348 0.03 0.022 Ti-254 51.3 12.2 47 2.1 256 5 20 306 0.04 0.88 ND 0.36 0.022 Ti-260 52.5 14.5 25.2 3.2 220 11 15 576 0.05 0.05 ND 0.2 0.062 Ti-262 40.8 12 137 4.52 292 76 25 318 0.06 0.22 ND 0.02 0.022 Ti-264 36.3 6.8 3.6 1.88 90 2 10 216 0.01 0.57 ND 0.01 0.582 Ti-284 57.2 21.3 41 1.32 256 17 30 284 0.05 2.4 ND 1.16 0.022 Ti-285 62.7 14 29 2.68 238 4 20 292 0.18 2.44 ND 0.71 0.022 Ti-292 8.1 2.1 78.5 1.24 146 25 5 244 0.13 0.14 ND 0.02 0.022

117 Ti-293 65 17.6 5.8 0.98 196 3 25 264 0.1 0.11 ND 0.03 0.022

Ti-294 15.1 3.3 442 4.1 326 566 ND 1060 ND 1.2 0.26 0.44 ND 0.03 Ti-294 45.1 9.6 763.8 5.22 276 846 ND 1706 0.11 0.39 ND 0.08 0.012 Ti-311 47 9.6 22 2.28 166 7 5 232 0.09 0.03 ND 0.02 0.102 Ti-328 54.7 13.1 8.1 2.14 176 3 10 250 0.07 0.04 ND 0.02 0.102 Ti-331 70.5 20.8 100.4 3.94 208 143 25 538 0.05 0.36 ND 0.06 0.022 Ti-335 78 14.7 5.9 1.84 218 4 20 286 0.1 0.06 ND 0.01 0.562 Ti-339 50.1 13.4 7 1.42 154 3 10 222 0.07 0.08 ND ND 0.642 Ti-340 51.7 12.7 7.4 1.3 164 3 20 218 0.09 0.07 ND ND 0.322 Ti-353 48.2 16.1 9.1 1.62 166 8 15 246 0.08 0.08 ND 0.03 0.062 Ti-368 57.7 12.3 7.1 2.48 154 13 20 240 0.08 0.06 ND 0.18 1.244 Ti-383 61.3 9 26.6 2.36 138 50 20 376 0.09 0.03 ND 0.02 0.782 Ti-399 25.6 6.4 5.7 0.9 23 47 ND 0.03 0.04 ND ND Ti-399 21.7 5.3 5.6 2.2 19 25 0.2 ND 3 0.02 ND 0.03 Ti-433 66.7 11.4 19.1 2.9 202 16 53 296 0.07 0.03 0.82 0.67 ND 0.52

117

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Ti-434 38.7 7.4 3.6 1.8 8 33 0.25 0.04 ND 0.05 Ti-448 69.3 5.5 6.7 1.2 18 35 ND 0.63 ND Ti-449 63 6.2 6.6 1.4 8 29 ND 0.2 0.33 0.25 ND Ti-454 50.3 17 35.2 1.9 2 44 0.1 ND 1.5 0.25 ND 0.39 Ti-459 36.5 6 8.9 1.7 13.6 21 ND 0.1 0.09 ND ND Ti-480 27.2 5.6 5.4 1.1 16 ND 0.6 0.2 0.23 0.09 ND ND Ti-498 97.1 16.9 128 3.6 162 193 91 830 0.1 2.2 0.74 1.6 ND 1.02 Ti-511 48 6.7 6.1 0.9 10 39 ND 0.1 2.92 ND ND 6.07 Ti-512 28.2 6.6 4 0.6 17 42 ND 6.65 ND ND 0.37

118 Ti-513 34.6 6.6 35.9 2 25 18 ND 0.6 0.13 0.63 ND 0.15

Ti-515 34.3 11.9 26.9 0.9 178 9 37 244 ND 0.176 0.54 0.218 ND 1.035 Ti-517 44.9 5.9 9.6 0.8 12 42 ND 0.7 0.35 0.12 ND 0.14 Ti-519 27.5 5.9 53.7 3.2 17 41 ND 0.4 0.34 1.14 ND 0.05 Ti-56 57.2 6.2 5.9 0.7 32 32 ND 0.2 0.17 0.13 ND ND Ti-576 0.0476 Ti-667 0.016 Ti-668 0.014 Ti-669 0.054 Ti-676 0.005 Ti-677 0.007 Ti-681 0.015 Ti-682 0.009 Ti-683 0.013 Ti-696 0.004

118

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Ti-721 0.01 Br-136 34.6 10.2 17.4 0.68 146 2 5 200 0.05 1.03 ND 0.33 0.022 Br-140 36.3 4.3 30.7 1.48 136 8 10 196 0.1 0.05 ND 0.01 0.902 Br-142 35.2 5.6 54.7 1.42 138 36 15 254 0.1 0.09 ND 0.01 3.74 Br-143 6.3 1.9 146.3 1.18 230 36 10 874 0.12 0.05 ND 0.01 0.022 Br-146 78.5 13.8 12.1 1.02 170 45 15 306 0.09 0.33 ND 0.45 1.424 Br-154 22 1.5 38.5 0.78 116 12 10 162 0.1 0.08 ND ND 0.784 Br-167 38 6 13.7 0.92 132 3 5 170 0.74 0.07 ND 0.01 0.422 Br-169 36.7 7 13.9 1.02 126 4 5 162 0.26 0.12 ND 0.01 2.202

119 Br-246 36.3 15.6 14.3 5.6 114 25 20 264 0.14 0.08 ND 0.03 2.422 Br-248 5.1 1.1 129.7 4.16 248 13 15 318 0.18 0.05 ND 0.03 0.042 Br-249 2.9 0.6 131.9 2.76 174 38 10 318 0.08 0.04 ND 0.02 0.022 Br-250 46 9.2 6.5 2.32 120 16 15 412 ND 0.33 ND 0.3 0.044 Br-251 43.5 11.1 22.8 5.16 164 6 20 246 0.14 0.12 ND 0.03 0.462 Br-256 39.1 5.5 12.4 1.68 128 5 10 164 2.62 0.32 ND 0.03 0.242 Br-267 28.4 3.1 43.1 2.92 128 47 10 224 0.05 0.06 ND ND 0.102 Br-268 20.1 3.2 4 1.56 42 5 15 94 0.06 0.04 ND ND 0.342 Br-272 54.4 9.9 28.2 2 68 55 35 680 0.92 0.05 ND 0.02 1.182 Br-275 38.7 7.4 66.4 3.8 172 47 20 282 0.05 0.32 ND 0.1 0.022 Br-331 134.7 45.6 34.1 2.64 298 2 250 738 0.75 0.23 ND 0.17 0.062 Br-336 48.8 8.7 7.7 1.24 136 11 15 242 0.09 0.98 ND 0.03 1.242 Br-350 22.4 3.6 118.6 3.84 190 74 15 132 0.63 0.34 0.0076 0.09 0.022 Br-390 9.2 2.1 35.3 1.1 21 20 ND 5.35 ND ND ND Br-527 25.5 3.6 31.1 3.24 154 2 5 190 0.18 0.06 ND 0.11 0.022

119

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Br-528 24.6 4 5 1.36 94 2 5 100 1.98 2.35 ND 0.12 0.132 Br-529 35.9 5.3 13.7 2.52 126 10 5 124 3.76 5.63 ND 0.11 2.416 Br-655 35.5 11.7 19.6 1.2 2 17 ND ND 2.26 0.1 ND 0.24 Br-675 47.6 4 5.3 0.8 7 31 ND 0.1 0.1 ND ND Br-721 40.9 19.4 4.8 6 8 29 24 2 56.4 0.69 0.072 7.37 Br-808 67.4 10 8.1 0.7 32 26 ND 0.3 0.04 0.14 ND ND Br-809 47 7.7 7.7 0.7 26 24 0.2 0.07 ND ND Br-810 74.1 12.9 9.1 0.7 38 41 0.2 0.2 0.85 ND 0.05 Br-862 0.004

120 Br-865 0.004 Br-873 0.005 Ly-112 30 17 Ly-479 8.4 1.8 2.9 0.56 13 10 10 76 0.03 ND ND ND 2.642 Ly-501 23.4 8.8 5.5 0.7 90 2 10 136 0.05 0.05 ND 0.02 0.022 Ly-518 15.5 4.6 8.3 1.26 20 22 ND 138 0.09 0.3 ND 0.13 4.842 Ly-519 6.1 2.9 3.5 0.42 7 7 ND 114 0.11 0.03 ND 0.02 5.062 Ly-520 18 6.9 8 0.34 58 3 5 94 0.14 0.03 0.0057 0.01 1.696 Ly-521 20.6 2.5 7.9 1.2 52 5 ND 106 0.09 0.15 ND ND 2.642 Ly-553 7.8 2 1 0.48 12 2 ND 20 0.06 0.05 ND 0.01 0.422 Ly-560 21 3.8 8.5 1.58 46 15 10 90 0.07 0.04 ND 0.01 1.822 Ly-561 31.9 4 6.6 0.86 100 2 5 106 0.06 0.08 0.0054 0.01 0.364 Ly-578 8.1 2.6 12.1 0.54 38 10 5 84 0.09 0.05 ND 0.01 0.762 Ly-579 11.4 2.3 2.4 0.48 42 2 ND 48 0.08 0.03 ND 0.01 0.082 Ly-580 31.1 3.6 9.1 2.42 96 9 9 126 0.03 0.15 ND 0.04 2.02

120

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Ly-581 28.9 4.1 4.7 0.66 90 2 ND 114 0.08 0.04 ND 0.01 0.542 Ly-583 48.2 7.3 10.3 1.32 102 29 10 254 0.09 0.04 ND 0.01 3.522 Ly-585 16.3 5.3 27.9 0.88 112 2 14 148 0.03 0.06 0.0237 0.01 0.482 Ly-628 28.6 3.7 10.8 0.42 100 3 3 110 0.03 0.04 ND ND 0.504 Ly-632 3 0.7 1.4 0.22 11 2 3 28 0.01 1.06 ND 0.02 0.862 Ly-635 11 1.6 2.7 0.22 28 3 7 42 0.09 0.04 ND 0.01 0.542 Ly-647 6.8 2.9 3.4 0.42 30 6 ND 108 0.06 0.12 ND 0.05 6.38 Ly-667 18.4 3.4 19.4 1.98 42 21 21 160 0.04 0.85 ND 0.1 3.74 Ly-668 2.4 0.5 1.1 0.52 6 2 2 18 0.08 0.07 ND 0.02 0.482

121 Ly-673 27.9 5.7 5.8 1.46 74 11 9 170 0.03 0.22 ND 0.03 0.98

Su-101 34.2 3.4 8.3 0.64 94 5 10 154 0.28 0.04 ND 0.01 1.556 Su-103 21.6 3 23.8 0.52 70 32 4 140 0.07 0.06 ND 0.01 0.482 Su-105 21.1 2.2 23.4 1.06 106 4 4 146 0.16 0.05 ND 0.09 1.058 Su-135 0.01 Su-55 26.4 3 8.5 0.48 74 6 16 134 0.05 0.07 0.005 0.08 0.182 Su-66 9 1.8 1.3 0.36 19 4 9 62 0.03 0.12 ND 0.05 0.782 Su-87 13.1 1.4 2.1 2.3 20 4 16 100 0.06 0.09 ND 0.03 1.564 Su-88 33 2.9 29.5 0.78 106 29 12 164 0.04 0.04 ND 0.01 0.842 Ti-104 8.9 7.5 Ti-104 9.4 8.8 0.1 Ti-107 16.6 3.6 78 2.8 120 82 16 366 0.188 0.187 0.15 0.45 ND 0.02 Ti-173 62.9 18 43 0.82 244 27 15 296 0.08 0.39 ND 1.47 0.022 Ti-174 35.4 4.5 18.5 1.26 132 4 5 130 0.01 0.16 ND 0.02 0.522 Ti-185 58.7 26.5 8.2 3.1 210 20 40 352 0.08 0.06 ND 0.01 0.222

121

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Ti-186 21.7 7.3 109 2.94 208 77 5 378 0.09 0.03 ND 0.04 0.022 Ti-199 48.1 24.1 4.6 2.3 224 4 42 208 0.1 0.04 ND 0.02 0.38 Ti-203 45.2 11.9 17.5 2.66 184 6 5 238 0.07 0.06 ND 0.09 0.042 Ti-204 36.3 11.7 6.2 1.46 110 10 10 172 0.05 0.05 ND 0.02 1.542 Ti-216 14.6 3.4 2.4 0.6 35 33 ND 0.1 0.03 0.06 ND ND Ti-236 48 15.8 14.3 3.76 200 7 15 250 0.03 0.1 ND 0.02 0.322 Ti-238 61.7 17.9 20.2 4.16 228 2 45 320 0.06 0.29 ND 0.04 0.022 Ti-242 41.7 5.6 7.1 0.96 130 4 5 166 0.03 0.06 ND 0.03 0.442 Ti-245 28.2 2.3 3.7 0.98 74 3 5 114 0.04 0.07 ND 0.01 0.722

122 Ti-257 25.1 3.9 170 3 118 240 15 638 0.06 0.69 0.0053 0.09 0.022

Ti-258 9.3 3.8 93 3.3 192 17 25 258 0.03 0.08 ND 0.02 0.02 Ti-268 7.4 1.4 0.8 0.6 15 2 5 48 0.07 0.14 ND ND 0.042 Ti-272 7.4 1.5 0.9 0.5 1 ND 0.16 ND ND ND Ti-275 16.8 2.6 2.8 0.76 36 3 5 80 0.15 0.09 ND ND 0.962 Ti-287 33.1 9.6 12.2 1.46 116 12 15 200 0.16 0.11 ND 0.01 0.102 Ti-308 32.5 5 23.7 1.14 156 4 5 228 0.07 0.03 ND 0.01 0.162 Ti-309 44.4 6.3 19.6 0.94 122 6 5 170 0.08 0.05 0.0059 0.17 0.262 Ti-310 33.9 13.1 37.7 1.44 190 7 5 242 0.1 0.11 ND 0.11 0.102 Ti-316 240 2.5 2.4 0.9 64 2 5 106 0.08 0.11 0.0111 0.01 0.202 Ti-321 1.9 0.5 121.6 0.9 168 29 10 254 0.08 0.11 0.0111 0.01 0.122 Ti-330 14.3 4.3 98.3 3.74 226 9 10 310 0.07 0.04 ND 0.02 0.142 Ti-336 39.2 17.2 233.7 3.32 328 77 130 682 0.09 0.08 ND 0.03 0.144 Ti-350 35.3 5.7 11.9 0.78 124 2 ND 152 0.42 0.48 ND 0.02 0.022 Ti-393 42.2 3.3 4.1 0.64 88 13 15 152 0.08 0.21 ND 1.03 0.56

122

Iron

TDS

Sulfate

Barium

Arsenic Nitrate

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Nitrite N as Magnesium Ti-396 42.2 2.6 31.2 0.74 102 22 5 144 0.1 0.03 ND 0.11 1.304 Ti-401 63.6 11 79 10.3 214 65 0.1 4.53 0.07 ND 0.59 Ti-445 34.8 7.7 20.7 2.2 44 ND 0.1 1.4 0.29 1 0.023 0.31 Ti-445 30.2 4.6 16.5 1.2 18 7 0.2 1.2 0.99 0.45 0.045 0.34 Ti-456 36.8 4.9 4 1.4 3.2 38 0.1 0.2 0.21 0.15 ND ND Ti-470 11.5 2.1 1.4 0.8 4 ND ND 0.11 0.02 ND ND Ti-471 6.1 1.3 1.3 0.8 4 10 0.2 0.11 ND ND ND Ti-479 15.3 2.8 7.1 1 28 2 ND 106 0.2 0.08 1.62 0.04 ND 0.08 Ti-481 45.4 6.6 8.3 1.1 19 ND ND 0.1 0.2 0.1 ND ND

123 Ti-482 7 1.4 1.1 0.6 18 1 ND 52 ND 0.06 1.12 0.03 ND ND Ti-485 6.2 1.5 0.2 0.3 3 ND ND ND 0.17 ND ND ND Ti-486 34.5 6.3 176 3.9 76 304 ND 588 ND 2.1 0.86 1.74 ND 0.05 Ti-516 31.8 3.5 3.1 0.5 5 41 ND 0.33 0.04 ND ND Ti-518 34.2 7.7 5.5 0.7 3 42 ND 0.2 0.1 0.21 ND ND Ti-534 47.3 5.1 6.3 1.1 14 29 ND 0.2 0.59 0.28 0.004 0.29 Ti-670 0.034 Ti-704 0.004

123

Date Sample ID Source Location Water Type Latitude Longitude Sampled Br-126 7/21/1981 PA Geological Survey Bradford Lock Haven 41.924 -76.822 Br-127 7/21/1981 PA Geological Survey Bradford Lock Haven 41.918 -76.834 Br-130 7/21/1981 PA Geological Survey Bradford Lock Haven 41.99 -76.853 Br-132 7/21/1981 PA Geological Survey Bradford Lock Haven 41.98611 -76.7742 Br-134 7/27/1981 PA Geological Survey Bradford Lock Haven 41.62583 -76.8681 Br-152 8/4/1981 PA Geological Survey Bradford Lock Haven 41.61306 -76.8583 Br-176 8/24/1981 PA Geological Survey Bradford Lock Haven 41.92 -76.653 Br-178 8/24/1981 PA Geological Survey Bradford Lock Haven 41.927 -76.669 Br-180 8/24/1981 PA Geological Survey Bradford Lock Haven 41.909 -76.659 Br-184 8/25/1981 PA Geological Survey Bradford Lock Haven 41.892 -76.677 Br-186 8/25/1981 PA Geological Survey Bradford Lock Haven 41.915 -76.698 Br-202 4/28/1986 USGS Bradford Lock Haven 41.80417 -76.655 Br-202 8/24/1981 PA Geological Survey Bradford Lock Haven 41.80417 -76.655 Br-203 8/24/1981 PA Geological Survey Bradford Lock Haven Br-204 8/24/1981 PA Geological Survey Bradford Lock Haven Br-205 4/28/1986 USGS Bradford Lock Haven 41.76333 -76.755 Br-205 8/25/1981 PA Geological Survey Bradford Lock Haven 41.76333 -76.755 Br-209 4/29/1986 USGS Bradford Lock Haven 41.75917 -76.7047 Br-238 4/29/1986 USGS Bradford Lock Haven 41.91306 -76.5397 Br-238 8/26/1981 PA Geological Survey Bradford Lock Haven 41.91306 -76.5397 Br-239 8/26/1981 PA Geological Survey Bradford Lock Haven 41.8975 -76.5686 Br-242 8/25/1981 PA Geological Survey Bradford Lock Haven 41.9225 -76.6117 Br-247 7/12/1982 PA Geological Survey Bradford Lock Haven 41.84333 -76.2353 Br-269 7/19/1982 PA Geological Survey Bradford Lock Haven 41.74417 -76.4861 Br-270 7/20/1982 PA Geological Survey Bradford Lock Haven 41.73861 -76.3581 Br-273 7/20/1982 PA Geological Survey Bradford Lock Haven 41.70917 -76.3153 Br-274 7/20/1982 PA Geological Survey Bradford Lock Haven 41.6975 -76.3131 Br-286 7/13/1982 PA Geological Survey Bradford Lock Haven 41.88222 -76.2158 Br-302 7/12/1982 PA Geological Survey Bradford Lock Haven 41.76306 -76.4294 Br-303 7/12/1982 PA Geological Survey Bradford Lock Haven 41.77194 -76.4094 Br-316 7/13/1982 PA Geological Survey Bradford Lock Haven 41.87306 -76.4006 Br-318 7/13/1982 PA Geological Survey Bradford Lock Haven 41.85194 -76.4903 Br-329 7/14/1982 PA Geological Survey Bradford Lock Haven 41.76639 -76.4719 Br-344 7/20/1982 PA Geological Survey Bradford Lock Haven 41.84944 -76.5208 Br-346 7/20/1982 PA Geological Survey Bradford Lock Haven 41.83889 -76.5819 Br-353 7/20/1982 PA Geological Survey Bradford Lock Haven 41.72806 -76.5647 Br-357 7/21/1982 PA Geological Survey Bradford Lock Haven 41.71861 -76.6858

124

Date Sample ID Source Location Water Type Latitude Longitude Sampled Br-362 7/21/1982 PA Geological Survey Bradford Lock Haven Br-376 7/21/1982 PA Geological Survey Bradford Lock Haven 41.71472 -76.3325 Br-377 7/21/1982 PA Geological Survey Bradford Lock Haven 41.71583 -76.3294 Br-378 7/21/1982 PA Geological Survey Bradford Lock Haven 41.71556 -76.335 Br-428 7/14/1982 PA Geological Survey Bradford Lock Haven 41.99306 -76.3136 Br-435 7/14/1982 USGS Bradford Lock Haven 41.93667 -76.3528 Br-441 7/15/1982 PA Geological Survey Bradford Lock Haven 41.90694 -76.2939 Br-448 7/20/1982 PA Geological Survey Bradford Lock Haven 41.9325 -76.4819 Br-476 7/20/1982 PA Geological Survey Bradford Lock Haven 41.97611 -76.4158 Br-489 7/21/1982 PA Geological Survey Bradford Lock Haven 41.91611 -76.4447 Br-496 7/21/1982 PA Geological Survey Bradford Lock Haven 41.85444 -76.3433 Br-503 7/21/1982 PA Geological Survey Bradford Lock Haven 41.85333 -76.2767 Br-510 7/21/1982 PA Geological Survey Bradford Lock Haven 41.79278 -76.3261 Br-552 4/28/1986 USGS Bradford Lock Haven 41.78694 -76.4542 Br-604 8/2/1983 USGS Bradford Lock Haven 41.77306 -76.4036 Br-606 8/2/1983 USGS Bradford Lock Haven 41.82222 -76.3589 Br-612 8/3/1983 USGS Bradford Lock Haven 41.77111 -76.4133 Br-620 8/4/1983 USGS Bradford Lock Haven 41.77278 -76.3989 Br-621 6/28/1984 USGS Bradford Lock Haven 41.97194 -76.7072 Br-622 8/4/1983 USGS Bradford Lock Haven 41.79444 -76.4139 Br-627 7/11/1984 USGS Bradford Lock Haven 41.93972 -76.7119 Br-630 8/4/1983 USGS Bradford Lock Haven 41.75583 -76.4231 Br-632 8/8/1983 USGS Bradford Lock Haven 41.77333 -76.4014 Br-633 6/27/1984 USGS Bradford Lock Haven 41.95861 -76.7172 Br-634 8/8/1983 USGS Bradford Lock Haven 41.77056 -76.415 Br-637 7/12/1984 USGS Bradford Lock Haven 41.97139 -76.7214 Br-639 6/27/1984 USGS Bradford Lock Haven 41.97222 -76.7183 Br-643 6/27/1984 USGS Bradford Lock Haven 41.98361 -76.7233 Br-648 8/10/1983 USGS Bradford Lock Haven 41.82806 -76.5114 Br-650 8/9/1983 USGS Bradford Lock Haven 41.82472 -76.5108 Br-651 6/28/1984 USGS Bradford Lock Haven 41.94556 -76.7078 Br-652 8/9/1983 USGS Bradford Lock Haven 41.82361 -76.51 Br-657 7/10/1984 USGS Bradford Lock Haven 41.84306 -76.8036 Br-659 7/11/1984 USGS Bradford Lock Haven 41.84444 -76.7997 Br-663 7/12/1984 USGS Bradford Lock Haven 41.85417 -76.8108 Br-664 8/10/1983 USGS Bradford Lock Haven 41.78889 -76.5397 Br-666 8/16/1983 USGS Bradford Lock Haven 41.99639 -76.4689

125

Date Sample ID Source Location Water Type Latitude Longitude Sampled Br-672 8/22/1983 USGS Bradford Lock Haven 41.99361 -76.4739 Br-673 7/12/1984 USGS Bradford Lock Haven 41.9225 -76.7919 Br-677 7/24/1984 USGS Bradford Lock Haven 41.95444 -76.7964 Br-684 8/17/1983 USGS Bradford Lock Haven 41.99167 -76.5633 Br-686 8/17/1983 USGS Bradford Lock Haven 41.99167 -76.5633 Br-687 7/24/1984 USGS Bradford Lock Haven 41.94972 -76.7981 Br-689 7/24/1984 USGS Bradford Lock Haven 41.94444 -76.795 Br-691 7/25/1984 USGS Bradford Lock Haven 41.94083 -76.7967 Br-692 8/17/1983 USGS Bradford Lock Haven 41.99861 -76.5753 Br-694 8/23/1983 USGS Bradford Lock Haven 41.99861 -76.5764 Br-695 7/25/1984 USGS Bradford Lock Haven 41.70611 -76.6519 Br-697 7/25/1984 USGS Bradford Lock Haven 41.70167 -76.5094 Br-700 8/17/1983 USGS Bradford Lock Haven 41.99861 -76.5794 Br-703 8/1/1984 USGS Bradford Lock Haven 41.75528 -76.6575 Br-705 8/1/1984 USGS Bradford Lock Haven 41.86972 -76.6358 Br-707 8/1/1984 USGS Bradford Lock Haven 41.86611 -76.67 Br-710 8/17/1983 USGS Bradford Lock Haven 41.99778 -76.5836 Br-713 8/1/1984 USGS Bradford Lock Haven 41.78583 -76.6144 Br-715 8/1/1984 USGS Bradford Lock Haven 41.78528 -76.6144 Br-723 8/7/1984 USGS Bradford Lock Haven 41.61583 -76.86 Br-726 8/16/1983 USGS Bradford Lock Haven 41.99861 -76.4656 Br-732 8/22/1983 USGS Bradford Lock Haven 41.96139 -76.5019 Br-747 4/28/1986 USGS Bradford Lock Haven 41.79333 -76.4558 Br-752 8/23/1983 USGS Bradford Lock Haven 41.905 -76.5594 Br-757 6/27/1984 USGS Bradford Lock Haven 41.93306 -76.7178 Br-764 6/13/1984 USGS Bradford Lock Haven 41.97111 -76.5342 Br-765 6/13/1984 USGS Bradford Lock Haven 41.97472 -76.5367 Br-766 6/13/1984 USGS Bradford Lock Haven 41.99917 -76.5339 Br-768 7/10/1984 USGS Bradford Lock Haven 41.98167 -76.5217 Br-779 6/28/1984 USGS Bradford Lock Haven 41.99389 -76.49 Br-806 7/17/1984 USGS Bradford Lock Haven 41.91111 -76.3161 Br-807 7/17/1984 USGS Bradford Lock Haven 41.86194 -76.2367 Br-854 6/6/2006 PADEP Bradford Lock Haven 41.92333 -76.83 Br-855 4/6/2006 PADEP Bradford Lock Haven 41.77194 -76.6006 Ly-510 8/4/1981 PA Geological Survey Lycoming Lock Haven 41.26 -76.808 Ly-592 8/18/1981 PA Geological Survey Lycoming Lock Haven 41.277 -77.093 Ly-594 8/18/1981 PA Geological Survey Lycoming Lock Haven 41.261 -77.108

126

Date Sample ID Source Location Water Type Latitude Longitude Sampled Ly-597 8/18/1981 PA Geological Survey Lycoming Lock Haven 41.327 -77.092 Ly-600 8/18/1981 PA Geological Survey Lycoming Lock Haven 41.295 -77.019 Ly-641 8/18/1981 PA Geological Survey Lycoming Lock Haven 41.293 -76.987 Ly-653 8/19/1981 PA Geological Survey Lycoming Lock Haven 41.277 -77.049 Ly-656 8/29/1981 PA Geological Survey Lycoming Lock Haven 41.269 -77.08 Su-126 8/31/1981 PA Geological Survey Sullivan Lock Haven 41.445 -76.744 Su-129 8/31/1981 PA Geological Survey Sullivan Lock Haven 41.48 -76.695 Ti-100 10/8/1975 PA Geological Survey Tioga Lock Haven 41.75361 -77.5603 Ti-101 10/23/1979 USGS Tioga Lock Haven 41.90611 -77.1531 Ti-101 5/30/1979 USGS Tioga Lock Haven 41.90611 -77.1531 Ti-102 5/31/1979 USGS Tioga Lock Haven 41.90306 -77.1442 Ti-102 10/23/1979 USGS Tioga Lock Haven 41.90306 -77.1442 Ti-103 5/31/1979 USGS Tioga Lock Haven 41.90194 -77.1344 Ti-103 10/23/1979 USGS Tioga Lock Haven 41.90194 -77.1344 Ti-105 5/31/1979 USGS Tioga Lock Haven 41.80972 -77.0825 Ti-105 10/24/1979 USGS Tioga Lock Haven 41.80972 -77.0825 Ti-108 10/23/1979 USGS Tioga Lock Haven 41.99194 -77.1436 Ti-108 5/30/1979 USGS Tioga Lock Haven 41.99194 -77.1436 Ti-109 5/30/1979 USGS Tioga Lock Haven 41.98917 -77.1506 Ti-109 10/23/1979 USGS Tioga Lock Haven 41.98917 -77.1506 Ti-110 5/30/1979 USGS Tioga Lock Haven 41.97611 -77.2322 Ti-110 10/23/1979 USGS Tioga Lock Haven 41.97611 -77.2322 Ti-182 7/7/1981 PA Geological Survey Tioga Lock Haven 41.88 -77.502 Ti-188 7/7/1981 PA Geological Survey Tioga Lock Haven 41.957 -77.59 Ti-191 7/13/1981 PA Geological Survey Tioga Lock Haven 41.74611 -77.4297 Ti-195 7/14/1981 PA Geological Survey Tioga Lock Haven 41.866 -77.544 Ti-200 7/15/1981 PA Geological Survey Tioga Lock Haven 41.996 -77.596 Ti-202 7/21/1981 PA Geological Survey Tioga Lock Haven 41.742 -77.323 Ti-229 7/20/1981 PA Geological Survey Tioga Lock Haven 41.99 -77.093 Ti-234 7/20/1981 PA Geological Survey Tioga Lock Haven 41.92528 -76.9858 Ti-246 7/21/1981 PA Geological Survey Tioga Lock Haven 41.77861 -76.9875 Ti-248 7/21/1981 PA Geological Survey Tioga Lock Haven 41.804 -77.02 Ti-252 7/21/1981 PA Geological Survey Tioga Lock Haven 41.73944 -77.0825 Ti-253 7/21/1981 PA Geological Survey Tioga Lock Haven 41.73861 -77.0822 Ti-254 7/21/1981 PA Geological Survey Tioga Lock Haven 41.74444 -77.0844 Ti-260 7/22/1981 PA Geological Survey Tioga Lock Haven 41.755 -77.252 Ti-262 7/22/1981 PA Geological Survey Tioga Lock Haven 41.76889 -77.285

127

Date Sample ID Source Location Water Type Latitude Longitude Sampled Ti-264 7/22/1981 PA Geological Survey Tioga Lock Haven 41.76944 -77.3536 Ti-284 7/21/1981 PA Geological Survey Tioga Lock Haven 41.93917 -77.4117 Ti-285 7/21/1981 PA Geological Survey Tioga Lock Haven 41.98639 -77.4842 Ti-292 7/27/1981 PA Geological Survey Tioga Lock Haven 41.975 -77.145 Ti-293 7/27/1981 PA Geological Survey Tioga Lock Haven 41.971 -77.235 Ti-294 4/28/1986 USGS Tioga Lock Haven 41.98528 -77.1525 Ti-294 7/28/1981 PA Geological Survey Tioga Lock Haven 41.98528 -77.1525 Ti-311 7/27/1981 PA Geological Survey Tioga Lock Haven 41.749 -77.235 Ti-328 7/27/1981 PA Geological Survey Tioga Lock Haven 41.784 -77.089 Ti-331 7/27/1981 PA Geological Survey Tioga Lock Haven 41.837 -77.007 Ti-335 7/28/1981 PA Geological Survey Tioga Lock Haven 41.775 -77.093 Ti-339 7/28/1981 PA Geological Survey Tioga Lock Haven 41.996 -76.94 Ti-340 7/28/1981 PA Geological Survey Tioga Lock Haven 41.994 -76.938 Ti-353 7/28/1981 PA Geological Survey Tioga Lock Haven 41.799 -77.144 Ti-368 8/5/1981 PA Geological Survey Tioga Lock Haven 41.563 -76.964 Ti-383 7/28/1981 PA Geological Survey Tioga Lock Haven 41.91389 -77.1469 Ti-399 7/10/1985 USGS Tioga Lock Haven 41.7925 -77.3022 Ti-399 11/7/1983 USGS Tioga Lock Haven 41.7925 -77.3022 Ti-433 7/27/1983 USGS Tioga Lock Haven 41.78389 -77.1608 Ti-434 7/27/1983 USGS Tioga Lock Haven 41.86278 -76.9558 Ti-448 8/8/1984 USGS Tioga Lock Haven 41.91194 -77.1425 Ti-449 8/8/1984 USGS Tioga Lock Haven 41.91139 -77.1425 Ti-454 8/14/1984 USGS Tioga Lock Haven 41.78694 -77.0119 Ti-459 8/14/1984 USGS Tioga Lock Haven 41.96139 -76.9244 Ti-480 6/6/1984 USGS Tioga Lock Haven 41.77222 -77.3797 Ti-498 8/1/1984 USGS Tioga Lock Haven 41.78972 -77.3044 Ti-511 7/24/1985 USGS Tioga Lock Haven 41.78583 -77.3025 Ti-512 7/31/1985 USGS Tioga Lock Haven 41.7925 -77.3008 Ti-513 12/4/1985 USGS Tioga Lock Haven 41.7925 -77.3003 Ti-515 7/10/1985 USGS Tioga Lock Haven 41.91306 -77.6047 Ti-517 7/10/1985 USGS Tioga Lock Haven 41.9575 -77.4169 Ti-519 7/11/1985 USGS Tioga Lock Haven 41.74417 -77.0775 Ti-56 7/9/1985 USGS Tioga Lock Haven 41.78944 -77.3028 Ti-576 7/1/2005 USGS Tioga Lock Haven 41.96194 -77.1089 Ti-667 6/15/2006 PADEP Tioga Lock Haven 41.98167 -76.9436 Ti-668 6/15/2006 PADEP Tioga Lock Haven 41.90667 -77.1433 Ti-669 6/15/2006 PADEP Tioga Lock Haven 41.98111 -76.9431

128

Date Sample ID Source Location Water Type Latitude Longitude Sampled Ti-676 6/6/2006 PADEP Tioga Lock Haven 41.90556 -77.1431 Ti-677 6/6/2006 PADEP Tioga Lock Haven 41.9075 -77.1389 Ti-681 5/6/2006 PADEP Tioga Lock Haven 41.98278 -76.9406 Ti-682 5/6/2006 PADEP Tioga Lock Haven 41.98111 -76.9425 Ti-683 5/6/2006 PADEP Tioga Lock Haven 41.98472 -76.9408 Ti-696 5/6/2006 PADEP Tioga Lock Haven 41.96056 -77.4456 Ti-721 4/6/2006 PADEP Tioga Lock Haven 41.96167 -77.3853 Br-136 7/27/1981 PA Geological Survey Bradford Catskill Br-140 7/28/1981 PA Geological Survey Bradford Catskill Br-142 7/28/1981 PA Geological Survey Bradford Catskill Br-143 7/28/1981 PA Geological Survey Bradford Catskill Br-146 7/29/1981 PA Geological Survey Bradford Catskill Br-154 8/4/1981 PA Geological Survey Bradford Catskill 41.604 -76.853 Br-167 5/25/1982 PA Geological Survey Bradford Catskill 41.56861 -76.2397 Br-169 5/25/1982 PA Geological Survey Bradford Catskill Br-246 7/13/1982 PA Geological Survey Bradford Catskill 41.77611 -76.1811 Br-248 7/13/1982 PA Geological Survey Bradford Catskill 41.70528 -76.1947 Br-249 7/13/1982 PA Geological Survey Bradford Catskill 41.68972 -76.1322 Br-250 7/14/1982 PA Geological Survey Bradford Catskill 41.69222 -76.2311 Br-251 7/14/1982 PA Geological Survey Bradford Catskill 41.63417 -76.2144 Br-256 7/19/1982 PA Geological Survey Bradford Catskill 41.60944 -76.4486 Br-267 7/19/1982 PA Geological Survey Bradford Catskill 41.67861 -76.4575 Br-268 7/19/1982 PA Geological Survey Bradford Catskill 41.69722 -76.4106 Br-272 7/20/1982 PA Geological Survey Bradford Catskill 41.67472 -76.2733 Br-275 7/21/1982 PA Geological Survey Bradford Catskill 41.67 -76.2797 Br-331 7/14/1982 PA Geological Survey Bradford Catskill 41.7575 -76.5397 Br-336 7/14/1982 PA Geological Survey Bradford Catskill 41.76639 -76.5961 Br-350 7/20/1982 PA Geological Survey Bradford Catskill 41.7 -76.5158 Br-390 4/29/1986 USGS Bradford Catskill 41.73028 -76.2353 Br-527 7/27/1982 PA Geological Survey Bradford Catskill 41.62278 -76.3708 Br-528 7/27/1982 PA Geological Survey Bradford Catskill 41.60417 -76.4511 Br-529 7/27/1982 PA Geological Survey Bradford Catskill 41.59139 -76.4244 Br-655 7/23/1984 USGS Bradford Catskill 41.86 -76.7756 Br-675 7/23/1984 USGS Bradford Catskill 41.77667 -76.8081 Br-721 8/7/1984 USGS Bradford Catskill 41.59778 -76.8747 Br-808 10/10/1985 USGS Bradford Catskill 41.65944 -76.2581 Br-809 10/29/1985 USGS Bradford Catskill 41.66056 -76.2575

129

Date Sample ID Source Location Water Type Latitude Longitude Sampled Br-810 10/30/1985 USGS Bradford Catskill 41.65917 -76.2603 Br-862 6/15/2006 PADEP Bradford Catskill 41.81167 -76.205 Br-865 6/15/2006 PADEP Bradford Catskill 41.77472 -76.7975 Br-873 3/6/2006 PADEP Bradford Catskill 41.58556 -76.3686 Ly-112 11/13/1991 USGS Lycoming Catskill 41.4075 -76.9956 Ly-479 4/30/1981 PA Geological Survey Lycoming Catskill 41.328 -77.16 Ly-501 6/1/1981 PA Geological Survey Lycoming Catskill 41.245 -77.178 Ly-518 8/4/1981 PA Geological Survey Lycoming Catskill 41.319 -76.844 Ly-519 8/4/1981 PA Geological Survey Lycoming Catskill 41.322 -76.83 Ly-520 8/5/1981 PA Geological Survey Lycoming Catskill 41.306 -76.823 Ly-521 8/5/1981 PA Geological Survey Lycoming Catskill 41.308 -76.756 Ly-553 8/3/1981 PA Geological Survey Lycoming Catskill 41.409 -77.251 Ly-560 8/4/1981 PA Geological Survey Lycoming Catskill 41.252 -77.328 Ly-561 8/4/1981 PA Geological Survey Lycoming Catskill 41.254 -77.323 Ly-578 8/5/1981 PA Geological Survey Lycoming Catskill 41.307 -77.173 Ly-579 8/5/1981 PA Geological Survey Lycoming Catskill 41.328 -77.159 Ly-580 8/10/1981 PA Geological Survey Lycoming Catskill 41.523 -77.088 Ly-581 8/4/1981 PA Geological Survey Lycoming Catskill 41.425 -77.186 Ly-583 8/4/1981 PA Geological Survey Lycoming Catskill 41.412 -77.218 Ly-585 8/11/1981 PA Geological Survey Lycoming Catskill 41.256 -77.169 Ly-628 8/10/1981 PA Geological Survey Lycoming Catskill 41.314 -76.687 Ly-632 8/11/1981 PA Geological Survey Lycoming Catskill 41.261 -76.487 Ly-635 8/12/1981 PA Geological Survey Lycoming Catskill 41.31 -76.742 Ly-647 8/18/1981 PA Geological Survey Lycoming Catskill 41.33 -76.936 Ly-667 8/17/1981 PA Geological Survey Lycoming Catskill 41.4 -77.458 Ly-668 8/17/1981 PA Geological Survey Lycoming Catskill 41.271 -77.287 Ly-673 8/18/1981 PA Geological Survey Lycoming Catskill 41.413 -77.476 Su-101 9/1/1981 PA Geological Survey Sullivan Catskill 41.518 -76.678 Su-103 9/1/1981 PA Geological Survey Sullivan Catskill 41.565 -76.611 Su-105 9/1/1981 PA Geological Survey Sullivan Catskill 41.545 -76.7 Su-135 3/6/2006 PADEP Sullivan Catskill 41.50889 -76.5667 Su-55 8/31/1981 PA Geological Survey Sullivan Catskill 41.321 -76.58 Su-66 9/1/1981 PA Geological Survey Sullivan Catskill 41.49 -76.609 Su-87 9/1/1981 PA Geological Survey Sullivan Catskill 41.54 -76.358 Su-88 9/1/1981 PA Geological Survey Sullivan Catskill 41.542 -76.346 Ti-104 5/30/1979 USGS Tioga Catskill 41.85806 -77.2378 Ti-104 10/24/1979 USGS Tioga Catskill 41.85806 -77.2378

130

Date Sample ID Source Location Water Type Latitude Longitude Sampled Ti-107 4/29/1986 USGS Tioga Catskill 41.85806 -77.2381 Ti-173 7/20/1981 PA Geological Survey Tioga Catskill 41.73139 -77.0969 Ti-174 7/20/1981 PA Geological Survey Tioga Catskill 41.722 -77.126 Ti-185 7/7/1981 PA Geological Survey Tioga Catskill 41.983 -77.568 Ti-186 7/7/1981 PA Geological Survey Tioga Catskill 41.93611 -77.5719 Ti-199 7/14/1981 PA Geological Survey Tioga Catskill 41.987 -77.573 Ti-203 7/21/1981 PA Geological Survey Tioga Catskill 41.749 -77.328 Ti-204 7/21/1981 PA Geological Survey Tioga Catskill 41.746 -77.359 Ti-216 7/9/1985 USGS Tioga Catskill 41.80389 -77.2931 Ti-236 7/21/1981 PA Geological Survey Tioga Catskill 41.856 -76.961 Ti-238 7/21/1981 PA Geological Survey Tioga Catskill 41.836 -76.96 Ti-242 7/21/1981 PA Geological Survey Tioga Catskill 41.76194 -76.9653 Ti-245 7/21/1981 PA Geological Survey Tioga Catskill 41.756 -76.958 Ti-257 7/21/1981 PA Geological Survey Tioga Catskill 41.842 -77.273 Ti-258 7/21/1981 PA Geological Survey Tioga Catskill 41.86028 -77.3081 Ti-268 7/27/1981 PA Geological Survey Tioga Catskill 41.75444 -77.4228 Ti-272 8/28/1985 USGS Tioga Catskill 41.77694 -77.3969 Ti-275 7/28/1981 PA Geological Survey Tioga Catskill 41.82 -77.196 Ti-287 7/21/1981 PA Geological Survey Tioga Catskill 41.943 -77.469 Ti-308 7/27/1981 PA Geological Survey Tioga Catskill 41.739 -77.117 Ti-309 7/27/1981 PA Geological Survey Tioga Catskill 41.737 -77.119 Ti-310 7/28/1981 PA Geological Survey Tioga Catskill 41.742 -77.233 Ti-316 7/28/1981 PA Geological Survey Tioga Catskill 41.68528 -77.4392 Ti-321 7/29/1981 PA Geological Survey Tioga Catskill 41.74 -77.434 Ti-330 7/27/1981 PA Geological Survey Tioga Catskill 41.83 -77.021 Ti-336 7/28/1981 PA Geological Survey Tioga Catskill 41.853 -76.984 Ti-350 7/28/1981 PA Geological Survey Tioga Catskill 41.822 -77.19 Ti-393 8/4/1981 PA Geological Survey Tioga Catskill 41.562 -77.211 Ti-396 8/4/1981 PA Geological Survey Tioga Catskill 41.57806 -77.1781 Ti-401 11/7/1983 USGS Tioga Catskill 41.84444 -77.2736 Ti-445 4/28/1986 USGS Tioga Catskill 41.69028 -77.2906 Ti-445 7/27/1983 USGS Tioga Catskill 41.69028 -77.2906 Ti-456 8/13/1984 USGS Tioga Catskill 41.82333 -77.2864 Ti-470 11/12/1985 USGS Tioga Catskill 41.77611 -77.3994 Ti-471 11/12/1985 USGS Tioga Catskill 41.77528 -77.4069 Ti-479 6/6/1984 USGS Tioga Catskill 41.77056 -77.3811 Ti-481 6/6/1984 USGS Tioga Catskill 41.79139 -77.3361

131

Date Sample ID Source Location Water Type Latitude Longitude Sampled Ti-482 6/6/1984 USGS Tioga Catskill 41.77778 -77.375 Ti-485 9/12/1985 USGS Tioga Catskill 41.77306 -77.4031 Ti-486 11/12/1985 USGS Tioga Catskill 41.77194 -77.4069 Ti-516 7/10/1985 USGS Tioga Catskill 41.82889 -77.2864 Ti-518 7/10/1985 USGS Tioga Catskill 41.81389 -77.1978 Ti-534 8/8/1984 USGS Tioga Catskill 41.84444 -77.2736 Ti-670 6/14/2006 PADEP Tioga Catskill 41.80111 -77.2267 Ti-704 4/6/2006 PADEP Tioga Catskill 41.77333 -76.9083

132

APPENDIX 2

Marcellus Shale Flow-back Data

133

Nitrite Nitrite

Iron

as N as

TDS

Sulfate

Barium

Arsenic

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Magnesium Nitrate

EOG Olysyn 21400.00 1420.00 24700.00 ND 190000.00 ND 280000.00 ND 3780.00 98.70 5726.00 818.00 ND 4.36 ND

EOG 8330.00 745.00 32500.00 ND 100000.00 ND 150000.00 ND 11500.00 27.40 3150.00 436.00 0.617 2.99 ND Housekneck Clear Spring 7610.00 603.00 21100.00 31.50 2040.00 1.40 Dairy 1H

F-Vargason 14500.00 1010.00 69400.00 228000.00 ND 337000.00 ND 8920.00 75.40 3400.00 898.00 ND ND 0.127

Black Unit 21300.00 1760.00 78400.00 28.00 192000.00 ND 333000.00 0.42 5030.00 74.20 5050.00 921.00 ND ND ND 1H

134 Sechrist 1H 8040.00 644.00 25200.00 115.00 64000.00 ND 104000.00 ND 4250.00 59.90 1890.00 400.00 ND 5.30 ND

Guinan Pad 8171.30 770.50 27729.00 117.00 67681.10 ND 141700.00 ND 7645.00 52.50 2158.00 ND 2.30 ND 2H Hoppaugh 7743.40 755.00 28792.00 139.00 69515.10 ND 148600.00 ND 7890.00 45.80 2055.00 ND 2.10 ND Pad 3H

Jackson 1H 9733.50 792.36 29869.50 52.00 97347.00 ND 176300.00 ND 11307.50 93.03 3440.00 ND 3.30 ND

Beardslee 2H 8514.50 829.10 27380.00 110.00 67351.60 ND 160200.00 ND 6796.00 54.10 2317.00 ND 2.30 ND

Marshlands 31900.00 1940.00 73200.00 8.00 151000.00 ND 358000.00 36.20 1160.00 280.00 4280.00 1980.00 ND 72.80 ND Unit #1 Pierson 801 2490.00 229.00 10600.00 82.00 24500.00 257.00 37300.00 0.40 813.00 10.50 661.00 ND 0.72 ND Pad 2H Temple Well 20500.00 1490.00 66200.00 ND 135000.00 ND 231000.00 0.20 4220.00 31.00 7890.00 953.00 ND 11.40 0.15 1H Jenzano Pad 609.70 ND 2885.60 88.00 5411.90 29.00 9212.00 ND 46.10 7.40 154.90 74.20 ND ND 0.47 8542H

134

Nitrite Nitrite

Iron

as N as

TDS

Sulfate

Barium

Arsenic

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Magnesium Nitrate Marquardt 6160.00 521.00 28500.00 20.00 59600.00 ND 95800.00 0.10 2190.00 65.80 1950.00 397.00 ND 3.42 ND Pad 8534H King Pad 478.30 ND 2767.70 175.00 4897.30 48.00 8520.00 9.60 11.70 34.70 66.30 64.00 ND 0.70 22 8499H

Flook 1H 7590.00 501.00 26200.00 163.00 110000.00 ND 105000.00 ND 5970.00 57.40 3160.00 625.00 ND 3.40 ND

Temple Tank 3030.90 175.70 13236.00 224.00 25905.20 ND 48600.00 ND 651.90 17.00 1017.60 379.00 ND 0.70 0.86

Poor Shot 2H 9570.00 571.00 28900.00 105.00 74300.00 ND 112000.00 6.80 6090.00 33.90 3580.00 512.00 ND 3.67 ND

135 Bower 4H 12700.00 714.00 42300.00 58.00 122000.00 ND 154000.00 ND 3930.00 24.80 3630.00 794.00 ND 7.05 ND

Bower 6H 13800.00 732.00 42700.00 58.00 82100.00 ND 154000.00 ND 3950.00 27.40 3840.00 533.00 ND

Flook 2H 22300.00 1510.00 47200.00 94.00 115000.00 ND 212000.00 ND 692.00 93.50 1610.00 921.00 ND 13.90 ND

Dog Run 4492.85 505.40 65631.68 255.15 91.50 116000.00 20.00 193943.88 2568.66 55.13 3209.41 4.05 NA Hunt Club 1H

Gentner 3H 18682.30 1339.66 50500.67 226.66 30.50 132000.00 7.00 229750.47 16715.40 110.62 10128.80 5.72 NA

Barto 1H 4020.00 367.00 19800.00 59.6 51900.00 82600.00 0.04 1290.00 35.20 1040.00 299.00 ND 1.98 ND

Lone Walnut 19784.70 1435.69 52222.44 265.42 30.50 136000.00 28.00 234949.95 14875.70 101.74 10196.40 8.85 3H

Clegg 722 4H 9740.00 569.00 22000.00 20.00 49700.00 ND 85700.00 6.80 4910.00 33.80 2390.00 400.00 0.038 5.31 0.27

135

Date Sample ID Source Location Water Type Sampled Latitude Longitude EOG Olysyn PA DEP Bradford Cnty Marcellus Flow-back 41.86014 -76.711781 EOG Housekneck PA DEP Bradford Cnty Marcellus Flow-back 41.85852 -76.687441 Clear Spring Dairy 1H PA DEP Bradford Cnty Marcellus Flow-back 41.76341 -76.534019 F-Vargason PA DEP Bradford Cnty Marcellus Flow-back 41.71007 -76.69489 Black Unit 1H PA DEP Bradford Cnty Marcellus Flow-back 41.73669 -76.603228 Sechrist 1H PA DEP Bradford Cnty Marcellus Flow-back 41.65839 -76.808777 Guinan Pad 2H PA DEP Bradford Cnty Marcellus Flow-back 41.8714 -76.692416 Hoppaugh Pad 3H PA DEP Bradford Cnty Marcellus Flow-back 41.87357 -76.680269 Jackson 1H PA DEP Bradford Cnty Marcellus Flow-back 41.8277 -76.702927 Beardslee 2H PA DEP Bradford Cnty Marcellus Flow-back 41.80979 -76.697886 Marshlands Unit #1 PA DEP Tioga Cnty Marcellus Flow-back 41.70408 -77.562421 Pierson 801 Pad 2H PA DEP Tioga Cnty Marcellus Flow-back 41.68958 -77.561163 Temple Well 1H PA DEP Lycoming Cnty Marcellus Flow-back 41.22161 -76.629613 Jenzano Pad 8542H PA DEP Lycoming Cnty Marcellus Flow-back 41.2596 -76.577797 Marquardt Pad 8534H PA DEP Lycoming Cnty Marcellus Flow-back 41.23415 -76.644055 King Pad 8499H PA DEP Lycoming Cnty Marcellus Flow-back 41.30806 -76.668405 Flook 1H PA DEP Lycoming Cnty Marcellus Flow-back 41.28213 -77.252175 Temple Tank PA DEP Lycoming Cnty Marcellus Flow-back 41.22161 -76.629613 Poor Shot 2H PA DEP Lycoming Cnty Marcellus Flow-back 41.33531 -77.164608 Bower 4H PA DEP Lycoming Cnty Marcellus Flow-back 41.28128 -76.631355 Bower 6H PA DEP Lycoming Cnty Marcellus Flow-back 41.28128 -76.631355 Flook 2H PA DEP Lycoming Cnty Marcellus Flow-back 41.28208 -77.252168 Dog Run Hunt Club 1H PA DEP Lycoming Cnty Marcellus Flow-back 41.33301 -77.291491 Gentner 3H PA DEP Lycoming Cnty Marcellus Flow-back 41.30231 -77.306562 Barto 1H PA DEP Lycoming Cnty Marcellus Flow-back 41.27089 -76.659691 Lone Walnut 3H PA DEP Lycoming Cnty Marcellus Flow-back 41.30523 -77.295583 Clegg 722 4H PA DEP Lycoming Cnty Marcellus Flow-back 41.58697 -76.860013

136

APPENDIX 3

Animal Waste, Septic Effluent, and Road Salt Data

137

Nitrite Nitrite

Iron

as N as

TDS

Sulfate

Barium

Arsenic

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Magnesium Nitrate Feedpen Min 194 28 130 226 97 882 Feedpen Max 1619 89 655 1352 648 22372 Feedpen Mean 698 69 408 761 450 5526 Ditch Influent Min 163 32 125 244 768 295 2048 0.10 Ditch Influent Max 218 45 219 322 1028 323 2164 7.51 Ditch Influent Mean 186 38 141 292 852 314 2106 2.57 Ditch Effluent Min 180 22 150 125 740 290 1236 0.02 Ditch Effluent Max 567 50 202 284 822 325 2204 1.35 Ditch Effluent Mean 269 37 182 207 791 308 1875 0.36

138 Waste Pond Min 95 12 76.2 85 610 186 565 0.01

Waste Pond Max 150 37 150 250 690 277 1884 0.37 Waste Pond Mean 152 25 120 182 500 240 1299 0.23 Am1 205 64 66 2 410 127 59 0.3 ND 0.53 0.515 0.01 Am2 127 32 45 2 412 33 15 0.09 ND 0.2 0.118 ND Am3 107 20 65 2 304 38 21 0.11 ND 0.19 0.132 ND Am4 113 44 102 2 410 51 36 0.1 ND 0.26 0.149 ND Am5 275 117 70 2 574 280 52 0.199 0.01 0.349 0.368 0.537 Am6 116 84 113 23 697 171 22 0.417 0.48 0.471 0.216 0.062 Am7 173 70 15 ND 269.6 50 75 0.128 ND 0.241 0.098 ND Am8 156 68 13 3 322.5 65 151 0.05 ND 0.177 0.107 0.671 Am9 192 100 27 6 526 69 236 0.103 ND 0.2 0.152 0.61 Am10 147 71 20 67 634 56 68 0.161 8.3 0.142 0.201 0.41 Am11 125 49 18 87 444 37 38 0.048 ND 0.151 0.084 0.08

138

Nitrite Nitrite

Iron

as N as

TDS

Sulfate

Barium

Arsenic

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Magnesium Nitrate GE-174A 67.00 18.00 23.00 2.60 180.00 41.00 52.00 330.00 <10 0.14 0.03 0.12 <.18 GE-234 33.00 10.00 15.00 3.20 100.00 32.00 12.00 194.00 0.56 0.26 0.02 0.07 <.18 GE-341 21.00 4.60 67.00 2.40 4.00 150.00 20.00 338.00 0.03 0.08 0.03 0.26 1.40 1-DG-5 30.00 9.40 110.00 1.30 260.00 12.00 0.01 0.06 0.01 1-DG-5 6.00 1.60 12.00 0.40 24.00 15.00 1-DG-WT 4.30 0.78 60.00 0.70 36.00 17.00 0.03 <.01 0.01 1.10 1-DG-WT 68.00 12.00 480.00 2.00 850.00 63.00 0.01 0.11 0.01 1-DG-WT 71.00 16.00 310.00 1.60 610.00 50.00 1-DG-WT 9.60 1.20 270.00 1.70 260.00 53.00

139 1-DG-WT 2.70 0.40 100.00 0.50 53.00 21.00

1-DG-WT 56.00 8.90 150.00 1.00 310.00 21.00 0.01 0.00 1-DG-WT 55.10 8.45 541.00 2.90 880.00 51.40 <10 <3 ALT-1-DG-5 19.00 4.80 37.00 0.50 110.00 13.00 ALT-1-DG-WT 47.00 11.00 100.00 0.40 230.00 15.00 ALT-1-DG-WT 17.00 2.40 270.00 0.90 260.00 70.00 ALT-1-DG-WT 4.20 0.62 89.00 0.20 24.00 23.00 ALT-1-DG-WT 21.00 3.70 58.00 0.30 63.00 18.00 0.01 <1 ALT-1-DG-WT 94.70 16.80 457.00 2.10 859.00 32.60 0.03 <3 2-DG-5 9.10 2.70 21.00 0.30 37.00 17.00 0.06 0.02 0.03 0.24 2-DG-5 1.50 0.48 17.00 0.10 7.90 12.00 0.02 0.00 2-DG-5 4.20 1.20 44.00 0.30 37.00 33.00 0.02 <10 2-DG-5 17.00 4.20 130.00 1.00 230.00 34.00 2-DG-5 6.80 1.80 35.00 0.80 56.00 16.00

139

Nitrite Nitrite

Iron

as N as

TDS

Sulfate

Barium

Arsenic

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Magnesium Nitrate 2-DG-5 49.70 15.40 106.00 1.30 297.00 9.10 0.01 2-DG-WT 6.20 1.70 100.00 0.50 62.00 31.00 0.01 <.01 <1 0.36 2-DG-WT 10.00 3.70 78.00 0.40 40.00 24.00 0.01 <.01 <1 2-DG-WT 5.10 1.70 56.00 0.40 65.00 8.10 0.06 0.04 2-DG-WT 4.80 1.40 52.00 0.20 40.00 17.00 2-DG-WT 11.00 4.60 66.00 0.30 24.00 24.00 2-DG-WT 29.00 7.80 220.00 1.00 340.00 26.00 2-DG-WT 25.00 7.10 170.00 <0.1 160.00 50.00 2-DG-WT 11.00 5.60 94.00 0.30 26.00 24.00 0.01 <1

140 2-DG-WT 18.10 6.70 115.00 0.40 148.00 13.40 0.01 <1

TW-2 270.00 48.00 4190.00 14.00 312.00 7000.00 160.00 12400.00 5.10 1.20 0.47 <0.02 TW-94D 200.00 40.00 2560.00 6.90 379.00 3930.00 150.00 7340.00 5.50 1.10 0.28 <.02 TW-94E 270.00 64.00 3110.00 14.00 249.00 5160.00 130.00 9320.00 4.10 1.10 0.43 <.02 MW-3 230.00 34.00 4420.00 18.00 244.00 7230.00 190.00 12800.00 4.00 0.80 0.58 <.02 MW-4 260.00 55.00 3980.00 15.00 326.00 7030.00 150.00 12400.00 5.00 0.80 0.42 <.02 MW-5 470.00 77.00 3690.00 19.00 194.00 6730.00 110.00 12500.00 5.60 0.60 0.42 <.02 MW-7 210.00 24.00 4400.00 14.00 209.00 7200.00 170.00 12600.00 3.10 1.30 0.38 <.02 MW-8 160.00 52.00 263.00 6.90 216.00 572.00 71.00 1520.00 2.50 0.20 0.24 <.02 MW-9 390.00 110.00 1320.00 12.00 171.00 2780.00 44.00 5870.00 5.50 0.90 0.88 <.02 MW-13 360.00 96.00 1440.00 13.00 272.00 3340.00 56.00 6670.00 5.10 0.40 0.52 <.02 MW-14 220.00 66.00 613.00 8.50 193.00 1350.00 36.00 2820.00 3.90 0.10 0.35 <.02 MW-15D 100.00 34.00 128.00 4.00 202.00 323.00 36.00 910.00 3.30 0.20 0.22 0.02 S1 166 80 218 3 475 416 46 0.129 0.2 0.152 0.255 0.028

140

Nitrite Nitrite

Iron

as N as

TDS

Sulfate

Barium

Arsenic

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Magnesium Nitrate S2 156 70 59 2 454 150 28 0.055 ND 0.107 0.096 ND S3 134 47 224 18 395 392 42 0.1 ND 0.37 0.102 0.01 S4 126 43 224 19 419 352 42 0.09 0.01 0.31 0.104 ND S5 92 34 111 7 363 219 30 0.025 ND 0.149 0.056 ND S6 100 44 54 4 296 229 35 0.023 0.22 0.115 0.054 0.003 S7 101 42 99 4 358 135 14 0.029 0.1 0.184 0.061 0.009 S8 122 60 92 4 427 169 26 0.081 ND 0.127 0.127 ND S9 121 63 59 8 353 167 41 0.055 ND 0.102 0.143 0.001

141 S10 73 32 204 7 421 170 48 0.036 0.03 0.069 0.076 ND S11 128 54 191 7 403 301 42 0.063 ND 0.14 0.151 ND

S12 100 49 42 ND 370 84 34 0.062 ND 0.124 0.05 ND S13 101 48 20 ND 275 44 137 0.055 0.16 0.203 0.036 0.114 RS1 35496 54015 4.002 RS2 241 29 6270 26 75 8930 248 0.192 0.01 1.27 0.63 0.04 GE-141 75.00 18.00 8.20 1.10 180.00 29.00 53.00 306.00 0.89 0.11 0.04 0.20 <.18 GE-349A 26.00 5.80 24.00 1.80 34.00 43.00 35.00 231.00 0.02 0.09 0.05 <3 2.20 GE-228 77.00 17.00 21.00 1.80 140.00 93.00 24.00 361.00 1.90 0.15 0.08 0.18 <.18 Wm:0-9 130.00 8.50 19.00 1.50 317.00 20.00 34.00 412.00 0.07 0.09 1.50 Wm:0-9 110.00 7.30 11.00 1.00 282.00 12.00 39.00 414.00 0.01 0.01 Wm:0-9 110.00 7.90 12.00 1.30 293.00 15.00 33.00 390.00 0.18 0.10 1.40 E1 495 300 2740 26 459 5620 19 0.38 0.22 5.65 1.04 0.13 E2 84 53 184 9 443 308 38 0.04 0.1 0.77 0.18 0.03 E3 84 19 416 11 402 504 52 0.1 0.11 0.22 0.28 0.03

141

Nitrite Nitrite

Iron

as N as

TDS

Sulfate

Barium

Arsenic

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Magnesium Nitrate E4 33 10 224 12 513 91 38 0.03 0.17 0.07 0.2 0.04 E5 64 23 262 22 501 253 73 0.03 0.45 0.14 0.11 0.53 E6 59 6.5 80 345 385 92 59 0.04 0.01 0.14 0.71 ND E7 60 41 46 17 598 35.5 22 0.13 0.07 0.66 0.09 0.07 E8 49 6 191 15 504 49.3 51 0.04 0.03 2.209 0.09 0.1 E9 46 22 98 23 139 91.7 92 0.03 0.09 0.17 0.14 0.04 E10 70 39 55 6 306 20.8 24 0.15 0.03 0.53 0.05 0.01 E11 67 26 89 17 327 69.1 95 0.06 ND 0.28 0.1 ND

142 E12 61 23 94 14 202 55.5 94 0.02 ND 0.21 0.06 ND

E13 69 24 115 17 346 84.3 130 0.02 ND 0.21 0.08 ND E14 71 24 89 12 210 86.7 112 0.06 ND 0.26 0.15 ND E15 68 26 79 18 130 61.5 107 0.05 ND 0.26 0.08 ND E16 68 26 70 16 117 63.2 77 0.05 ND 0.25 0.06 ND E17 73 24 69 9 150 79 97 0.07 ND 0.28 ND ND E18 118 24 77 28 118 147 84 0.05 ND 0.28 ND E19 70 27 82 18 203 66.5 109 0.05 ND 0.3 0.22 ND E20 120 27 82 16 264 118 94 0.03 ND 0.35 ND E21 67 24 88 16 261 67.5 109 0.04 ND 0.28 0.12 ND E22 89 26 90 25 196 110 97 0.4 ND 0.3 ND 0.01 E23 27 2.3 46 257 ND 88.9 84 0.02 ND 0.11 0.07 ND E24 66 24 255 33 368 312 92 0.1 1.12 0.29 0.1 E25 107 26 88 23 ND 30.8 26 0.08 2.93 0.34 0.07 0.29 E26 112 25 399 12 608 618 12 0.06 0.9 0.24 0.36 0.26

142

Nitrite Nitrite

Iron

as N as

TDS

Sulfate

Barium

Arsenic

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Magnesium Nitrate E27 34 7 124 281 416 123 82 0.05 0.2 0.15 0.05 0.13 E28 142 21 70 8 487 105 8.4 0.1 0.8 0.26 0.09 0.1 E29 17 7.5 393 6 472 324 48 0.42 ND 0.78 Em1 105 45 21 3 341 50.6 54 0.03 ND 0.12 0.1 0.01 Em2 101 43 19 4 333 39.7 56 0.03 ND 0.1 0.08 ND Em3 111 47 75 13 387 116 77 0.08 0.04 0.24 0.29 0.19 Tile Effluent1 40.00 14.00 98.00 12.00 365.00 45.00 27.00 Plume Core1 90.00 17.00 86.00 11.00 276.00 24.00 63.00 1.00 Tile Effluent2 14.00 3.00 90.00 21.00 316.00 55.00 42.00 33.00

143 Plume Core2 44.00 3.00 45.00 14.00 12.00 38.00 32.00 0.10

MW-11D 58.00 17.00 24.00 2.30 173.00 24.00 69.00 336.00 0.80 <.05 0.82 <.02

143

Date Sample ID Source Location Water Type Sampled Feedpen Min 1969 EPA McKinney, Texas Animal Waste Feedpen Max 1969 EPA McKinney, Texas Animal Waste Feedpen Mean 1969 EPA McKinney, Texas Animal Waste Ditch Influent Min 1969 EPA McKinney, Texas Animal Waste Ditch Influent Max 1969 EPA McKinney, Texas Animal Waste Ditch Influent Mean 1969 EPA McKinney, Texas Animal Waste Ditch Effluent Min 1969 EPA McKinney, Texas Animal Waste Ditch Effluent Max 1969 EPA McKinney, Texas Animal Waste Ditch Effluent Mean 1969 EPA McKinney, Texas Animal Waste Waste Pond Effluent Min 1969 EPA McKinney, Texas Animal Waste Waste Pond Effluent Max 1969 EPA McKinney, Texas Animal Waste Waste Pond Effluent Mean 1969 EPA McKinney, Texas Animal Waste Am1 2005 Illinois Geol Survey Monroe Cnty, IL Animal Waste Am2 2005 Illinois Geol Survey Monroe Cnty, IL Animal Waste Am3 2005 Illinois Geol Survey Monroe Cnty, IL Animal Waste Am4 2005 Illinois Geol Survey Monroe Cnty, IL Animal Waste Am5 2005 Illinois Geol Survey McHenry Cnty, IL Animal Waste Am6 2005 Illinois Geol Survey McHenry Cnty, IL Animal Waste Am7 2005 Illinois Geol Survey Bloomington, IL Animal Waste Am8 2005 Illinois Geol Survey Bloomington, IL Animal Waste Am9 2005 Illinois Geol Survey McHenry Cnty, IL Animal Waste Am10 2005 Illinois Geol Survey McHenry Cnty, IL Animal Waste Am11 2005 Illinois Geol Survey McHenry Cnty, IL Animal Waste GE-174A 06/14/99 USGS Geauga Cnty, OH Road Salt GE-234 06/21/99 USGS Geauga Cnty, OH Road Salt GE-341 06/23/99 USGS Geauga Cnty, OH Road Salt 1-DG-5 03/28/95 USGS Beverly Shores, IN Road Salt 1-DG-5 05/07/96 USGS Beverly Shores, IN Road Salt 1-DG-WT 12/12/94 USGS Beverly Shores, IN Road Salt 1-DG-WT 03/28/95 USGS Beverly Shores, IN Road Salt 1-DG-WT 05/07/96 USGS Beverly Shores, IN Road Salt 1-DG-WT 08/14/96 USGS Beverly Shores, IN Road Salt 1-DG-WT 11/07/96 USGS Beverly Shores, IN Road Salt 1-DG-WT 02/11/97 USGS Beverly Shores, IN Road Salt 1-DG-WT 05/20/97 USGS Beverly Shores, IN Road Salt ALT-1-DG-5 05/07/96 USGS Beverly Shores, IN Road Salt ALT-1-DG-WT 05/07/96 USGS Beverly Shores, IN Road Salt

144

Date Sample ID Source Location Water Type Sampled ALT-1-DG-WT 08/14/96 USGS Beverly Shores, IN Road Salt ALT-1-DG-WT 11/07/96 USGS Beverly Shores, IN Road Salt ALT-1-DG-WT 02/11/97 USGS Beverly Shores, IN Road Salt ALT-1-DG-WT 05/20/97 USGS Beverly Shores, IN Road Salt 2-DG-5 12/20/94 USGS Beverly Shores, IN Road Salt 2-DG-5 04/04/95 USGS Beverly Shores, IN Road Salt 2-DG-5 11/01/95 USGS Beverly Shores, IN Road Salt 2-DG-5 08/19/96 USGS Beverly Shores, IN Road Salt 2-DG-5 11/06/96 USGS Beverly Shores, IN Road Salt 2-DG-5 05/15/97 USGS Beverly Shores, IN Road Salt 2-DG-WT 12/20/94 USGS Beverly Shores, IN Road Salt 2-DG-WT 04/04/95 USGS Beverly Shores, IN Road Salt 2-DG-WT 11/01/95 USGS Beverly Shores, IN Road Salt 2-DG-WT 02/07/96 USGS Beverly Shores, IN Road Salt 2-DG-WT 05/09/96 USGS Beverly Shores, IN Road Salt 2-DG-WT 08/19/96 USGS Beverly Shores, IN Road Salt 2-DG-WT 11/06/96 USGS Beverly Shores, IN Road Salt 2-DG-WT 02/19/97 USGS Beverly Shores, IN Road Salt 2-DG-WT 05/15/97 USGS Beverly Shores, IN Road Salt TW-2 Mar-98 USGS Valparaiso, IN Road Salt TW-94D Mar-99 USGS Valparaiso, IN Road Salt TW-94E Mar-00 USGS Valparaiso, IN Road Salt MW-3 Mar-01 USGS Valparaiso, IN Road Salt MW-4 Mar-02 USGS Valparaiso, IN Road Salt MW-5 Mar-03 USGS Valparaiso, IN Road Salt MW-7 Mar-04 USGS Valparaiso, IN Road Salt MW-8 Mar-05 USGS Valparaiso, IN Road Salt MW-9 Mar-06 USGS Valparaiso, IN Road Salt MW-13 Mar-08 USGS Valparaiso, IN Road Salt MW-14 Mar-09 USGS Valparaiso, IN Road Salt MW-15D Mar-10 USGS Valparaiso, IN Road Salt S1 2005 Illinois Geol Survey Hampshire, IL Road Salt S2 2005 Illinois Geol Survey Hampshire, IL Road Salt S3 2005 Illinois Geol Survey South Elgin, IL Road Salt S4 2005 Illinois Geol Survey South Elgin, IL Road Salt S5 2005 Illinois Geol Survey Marengo, IL Road Salt S6 2005 Illinois Geol Survey Marengo, IL Road Salt

145

Date Sample ID Source Location Water Type Sampled S7 2005 Illinois Geol Survey Union, IL Road Salt S8 2005 Illinois Geol Survey Wonder Lake, IL Road Salt S9 2005 Illinois Geol Survey McHenry Cnty, IL Road Salt S10 2005 Illinois Geol Survey Johnsburg, IL Road Salt S11 2005 Illinois Geol Survey Wonder Lake, IL Road Salt S12 2005 Illinois Geol Survey Wonder Lake, IL Road Salt S13 2005 Illinois Geol Survey Paxton, IL Road Salt RS1 2005 Illinois Geol Survey Kane Cnty, IL Road Salt RS2 2005 Illinois Geol Survey Western Springs, IL Road Salt GE-141 6/15/1999 USGS Geauga Cnty, OH Septic GE-349A 7/1/1999 USGS Geauga Cnty, OH Septic GE-228 6/30/1999 USGS Geauga Cnty, OH Septic Wm:0-9 5/11/1988 USGS Williamson Cnty, TN Septic Wm:0-9 11/21/1988 USGS Williamson Cnty, TN Septic Wm:0-9 5/9/1989 USGS Williamson Cnty, TN Septic E1 2005 Illinois Geol Survey Monroe Cnty, IL Septic E2 2005 Illinois Geol Survey Monroe Cnty, IL Septic E3 2005 Illinois Geol Survey Monroe Cnty, IL Septic E4 2005 Illinois Geol Survey Monroe Cnty, IL Septic E5 2005 Illinois Geol Survey Monroe Cnty, IL Septic E6 2005 Illinois Geol Survey Monroe Cnty, IL Septic E7 2005 Illinois Geol Survey Monroe Cnty, IL Septic E8 2005 Illinois Geol Survey Monroe Cnty, IL Septic E9 2005 Illinois Geol Survey Monroe Cnty, IL Septic E10 2005 Illinois Geol Survey Monroe Cnty, IL Septic E11 2005 Illinois Geol Survey Monroe Cnty, IL Septic E12 2005 Illinois Geol Survey Monroe Cnty, IL Septic E13 2005 Illinois Geol Survey Monroe Cnty, IL Septic E14 2005 Illinois Geol Survey Monroe Cnty, IL Septic E15 2005 Illinois Geol Survey Monroe Cnty, IL Septic E16 2005 Illinois Geol Survey Monroe Cnty, IL Septic E17 2005 Illinois Geol Survey Monroe Cnty, IL Septic E18 2005 Illinois Geol Survey Monroe Cnty, IL Septic E19 2005 Illinois Geol Survey Monroe Cnty, IL Septic E20 2005 Illinois Geol Survey Monroe Cnty, IL Septic E21 2005 Illinois Geol Survey Monroe Cnty, IL Septic E22 2005 Illinois Geol Survey Monroe Cnty, IL Septic

146

Date Sample ID Source Location Water Type Sampled E23 2005 Illinois Geol Survey Monroe Cnty, IL Septic E24 2005 Illinois Geol Survey Monroe Cnty, IL Septic E25 2005 Illinois Geol Survey Monroe Cnty, IL Septic E26 2005 Illinois Geol Survey Monroe Cnty, IL Septic E27 2005 Illinois Geol Survey Monroe Cnty, IL Septic E28 2005 Illinois Geol Survey Monroe Cnty, IL Septic E29 2005 Illinois Geol Survey Monroe Cnty, IL Septic Em1 2005 Illinois Geol Survey South Elgin, IL Septic Em2 2005 Illinois Geol Survey South Elgin, IL Septic Em3 2005 Illinois Geol Survey South Elgin, IL Septic Tile Effluent1 1989 Univ. of Waterloo Cambridge, Ontario Septic Plume Core1 1989 Univ. of Waterloo Cambridge, Ontario Septic Tile Effluent2 1989 Univ. of Waterloo Muskoka, Ontario Septic Plume Core2 1989 Univ. of Waterloo Muskoka, Ontario Septic MW-11D Mar-07 USGS Valparaiso, IN Septic

147

APPENDIX 4

2012-2013 Ground Water Sample Data

148

Nitrite Nitrite

Iron

as N as

TDS

Sulfate

Barium

Arsenic

Sodium

Calcium

Chloride Bromide

Strontium

Alkalinity

Potassium

Sample Sample ID

Aluminum

Manganese

Magnesium Nitrate BR-1 31.8 7.5 82.3 1.4 200 74.9 2.04 158 ND 0.995 0.384 0.605 ND ND 0.114 ND BR-2 31.8 7.74 46.7 2.04 157 34.2 14.5 200 ND 0.404 0.0259 0.666 ND 0.0113 0.0666 ND BR-3 21.4 4.51 60.8 1.65 173 22.9 5.61 22 ND 0.706 0.0935 1.46 ND ND 0.0485 0.481 BR-4 68.3 15.4 27.5 1.14 200 2.45 84.4 312 ND 0.0811 0.946 0.288 ND 0.0107 0.438 ND BR-5 12.4 2.04 124 2.12 228 51.6 ND 346 ND 0.898 0.0459 1.76 0.349 ND ND ND BR-6 24.2 5.36 83.5 2.29 226 23 1.52 310 ND 1.46 0.221 2.66 0.184 ND 0.0182 ND BR-7 53.4 8.35 9.39 1.98 142 19 14.2 232 ND 0.0511 0.0535 0.0817 ND ND ND 2.82 BR-8 30 10.9 27.7 2.15 140 2.68 21.3 129 ND 0.224 0.0157 0.922 ND ND 0.0342 ND BR-9 63.4 13.5 21.2 0.884 206 1.94 43.4 285 ND 0.0485 1.3 0.149 ND ND 0.0378 ND BR-10 46.6 5.56 10.1 1.72 128 12.8 13.1 197 ND 0.388 ND 1.34 ND 0.00303 ND 1.64

149 Ly-1 72.3 8.76 3.49 0.891 158 7.82 26 276 0.0206 0.0623 0.0277 0.163 ND ND ND 5.15

Ly-2 9.81 3.02 36.7 ND 77.5 25 1.72 76 0.021 0.159 0.135 0.447 ND ND 0.0733 ND Su-1 19.1 4.16 0.875 0.779 68.6 2.7 4.97 12 ND 0.0641 0.0874 0.0577 ND 0.00148 2.06 ND Tioga-1 13.1 4.91 2.19 1.27 47.3 2.88 8.65 70 0.534 0.046 0.24 0.101 ND 0.00471 ND 0.449 Tioga-2 60.2 10.9 48.9 2.59 202 49.2 15.9 290 ND 0.492 0.078 0.442 ND 0.00121 ND 0.819 Tioga-3 19.3 8.48 3.46 1.57 83.7 2.44 9.5 65 0.311 0.182 0.395 0.103 ND 0.00461 0.288 ND Tioga-4 29 5.86 53.5 2.33 208 5.29 9.81 242 ND 0.253 0.0621 1.25 ND ND 0.0278 ND Tioga-5 86.6 24.5 40.4 1.53 396 10.5 13.5 396 ND 0.296 1.98 0.486 ND 0.0508 1.51 ND Tioga-6 84.4 31 31.6 4.18 282 8.52 109 432 ND 0.0239 0.251 1.12 ND 0.00158 0.37 ND Tioga-7 60.1 12 14.5 3.45 198 5.75 24 116 ND 0.093 ND 0.602 ND ND ND ND Tioga-8 73.7 11.7 40 4.27 96 93.9 27.2 410 0.0221 0.559 0.0123 0.628 0.137 0.00112 0.165 14.1

149

Date Sample ID Source Location Water Type Sampled BR-1 12/18/2012 Reilly Bradford Lock Haven BR-2 12/22/2012 Reilly Bradford Lock Haven BR-3 12/23/2012 Reilly Bradford Lock Haven BR-4 1/4/2013 Reilly Bradford Lock Haven BR-5 2/8/2013 Reilly Bradford Lock Haven BR-6 2/8/2013 Reilly Bradford Lock Haven BR-7 2/9/2013 Reilly Bradford Lock Haven BR-8 2/10/2013 Reilly Bradford Lock Haven BR-9 2/10/2013 Reilly Bradford Lock Haven BR-10 2/23/2013 Reilly Bradford Catskill Ly-1 1/9/2013 Reilly Lycoming Onondaga & Old Port Ly-2 2/23/2013 Reilly Lycoming Trimmers Rock Su-1 12/23/2012 Reilly Sullivan Huntley Mountain Tioga-1 12/19/2012 Reilly Tioga Catskill Tioga-2 12/19/2012 Reilly Tioga Lock Haven Tioga-3 12/19/2012 Reilly Tioga Catskill Tioga-4 12/20/2012 Reilly Tioga Lock Haven Tioga-5 12/20/2012 Reilly Tioga Lock Haven Tioga-6 1/6/2013 Reilly Tioga Lock Haven Tioga-7 1/6/2013 Reilly Tioga Lock Haven Tioga-8 2/11/2013 Reilly Tioga Catskill

150