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The Marcellus Shale: Shallow Water Aquifers Amanda Murphy- 951533915 Geosciences 452- Introduction to Hydrogeology Fall 2013 Instructors: Richard R. Parizek, Professor of Hydrogeology James D. Kubicki, Professor of Geochemistry

ABSTRACT: This study was conducted in 2012 by members of the Proceedings of the National Academy of Sciences of the United States of America (PNAS). The purpose of this study is to present geological and chemical evidence from numerous studies to prove that hydraulic fracturing (commonly known as fracking) fluids are leaking into shallow drinking water aquifers. The research uses molar ratios and concentrations from regions of northeastern Pennsylvania. Ground water samples were collected from the Alluvium, Catskill, and Lock Haven aquifers. The existing evidence suggest these areas are at risk of shallow water aquifer contamination.

Introduction
Hydraulic fracturing (more commonly known as fracking) fluids used in the drilling of the Marcellus Shale are the source of various debates and established controversies sparked by the people and government of Pennsylvania. The people of Pennsylvania are fighting to discover the truth to these questions. There have been, and still are numerous studies being conducted. In 2012 members of the Proceedings of the National Academy of Sciences of the United States of America (PNAS) decided to explore the possibility of hydraulic fracturing fluids leaking into shallow aquifers of Pennsylvania. The authors of the case study included: Nathaniel Warner, Robert Jackson, Thomas Darrah, Alissa White, Avner Vengosh (Division of Earth and Ocean Sciences, Nicholas School of Environment, Duke University, North Carolina) and Adrian Down, Kaiguang Zhao (Center on Global Change, Nicholas School of Environment, Duke University, North Carolina), and Stephen Osborne (Geological Sciences Department, California State Polytechnic University, California). This report supplements the PNAS report and focuses on the issues associated with fracking fluids: the possibility of them leaking into shallow drinking water aquifers, specifically focusing on chemical evidence. The geochemical evidence presented primarily represents regions of northeastern Pennsylvania (NE PA). In preparing this report, I relied on literature review, numerical modeling simulations, my personal knowledge on the fracking process, course notes, and the integration of chemical data (Br, Cl, Na, Ba, Sr, and Li) and isotopic ratios (87Sr86Sr, 2HH, 18O16O, and 228Ra226Ra). The data from the PNAS report and previous studies in 426 shallow ground water samples and eighty-three northern Appalachian brine samples suggests that mixing relationships between

3 shallow ground water and a deep formation brine causes ground water salinization in some locations 1. Ground water was sampled from the Alluvium, Catskill, and Lock Haven aquifers. This salinized ground water was found to have a strong geochemical fingerprint (Cl > 20mg /L). Since the water had such a high concentration, it is possible that Marcellus brine is migrating through naturally occurring pathways within the aquifers.

It is important to keep in mind that, the occurrences of the saline water do not correlate with the location of shale-gas wells. These occurrences are also consistent with reported data before rapid shale-gas development in northeastern regions. However, the presence of these fracking fluids suggests that the aquifers have conductive pathways, and regimes in northeastern Pennsylvania are at greater risk for contamination of shallow drinking water sources because of natural connections to deeper hydraulic formations.

Background
The United States possess vast natural gas resources that would not be obtainable if not for hydraulic fracturing and advances in horizontal drilling. So, how does hydraulic fracturing work? In many places worldwide, natural gas is trapped in rocks, so it cannot be easily produced using conventional gas well drilling and production practices. In conventional formations, natural gas flows freely into a gas well through porous rock. Figure 1a shows a conventional gas well 2. In low permeability formations, natural gas is trapped in the pores and micro-fractures and cannot flow into the gas well; hence, hydraulic fracturing. Hydraulic fracturing is a method of

4 inducing manmade fractures in lowpermeability rocks, so that the trapped natural gas can flow from the rock, into the fractures, and into the natural gas well 3. In Figure 1b a horizontal well with hydraulic fractures is depicted. It can be inferred from Figure 1b that drilling a well horizontally in a formation increases the length of the well casing that can drain gas from the formation. The U.S. Energy
Figure 1a. Conventional gas well

Information Administration estimates

Figure 1b. Unconventional gas well

that shale formations in the United States contain 827 trillion cubic feet of recoverable natural gas. If it were not for advances in horizontal drilling, these resources would not be obtainable. There is an increased awareness regarding the potential for contamination in the shallow drinking water aquifers of the Appalachian basin of northeastern Pennsylvania due to the extraction of natural gas from the Marcellus Shale 4-5. The debate regarding the safety of shale extraction has focused on the potential for contamination from toxic substances in hydraulic fracturing fluid and/or produced brines during drilling, transport, and disposal 9-12. Recent findings in NE PA demonstrated that shallow water wells that are in close proximity to natural gas wells (<1 km) yielded higher concentrations of methane, ethane, and propane with thermogenic isotopic characteristics. Comparatively, wells further away from natural gas development had lower combustible gas concentrations and isotopic characteristics consistent

5 with a mixture between a thermogenic and biogenic components 7. Increasing reports of changes in drinking water have increasingly been blamed on the rapid rate of shale gas development.

Figure 2. Digital elevation model (DEM) map of northeastern PA. Shaded brown areas indicate higher elevations and blue-green shaded areas indicate lower elevations (valleys). The distribution of shallow (<90 m) groundwater samples from this study and previous studies (18, 19) are labeled based on water type. Two low salinity (Cl <20 mg/L) water types dominated by Ca-HCO3 (type A = green circles) or Na-HCO3 (type B = blue triangles) were the most common, and two higher salinity (Cl > 20 mg/L) water types were also observed: Br/Cl < 0.001 (type C = pink squares) and brine-type groundwater Br/Cl > 0.001 (type D = red diamonds). Type D groundwater samples appear associated with valleys (Table S.1) and are sourced from conservative mixing between a brine and fresh meteoric water. The DEM data were obtained from NASA Shuttle Radar Topography Mission http://srtm.usgs.gov/.

The study area in northeastern Pennsylvania consist of six counties (Figure 2) the Appalachian Plateaus physiographic province in the structurally and tectonically complex transition between the highly deformed Valley and Ridge Province and the less deformed Appalachian Plateau 15-16. The study area contains a surficial cover composed of a mix of unconsolidated glacial till, outwash, alluvium and deltaic sediments, and postglacial deposits (the Alluvium aquifer) that are thicker in the valleys (Figure S.1) 20-22. These sediments are underlain by Upper Devonian through Pennsylvanian age sedimentary sequences that are gently folded and dip shallowly (1

6 3) to the east and south (Figure S.2). The two major bedrock aquifers are the Upper Devonian Catskill and the underlying Lock Haven Formations 17, 18, 21, 22. The average depth of drinking water wells in the study area is between 60 and 90 meters (Table S.1). The underlying geological formations, including the Marcellus Shale (at a depth of 1,2002,500 meters below the surface) are presented in Figure 2, Figure S.2A, and Figure S.2B. In this study, PNAS analyzed the geochemistry of 109 newly-collected water samples and 49 wells from the previous study 7 from the three principal aquifers, Alluvium (n = 11), Catskill (n = 102), and Lock Haven (n = 45), categorizing these waters into four types based on their salinity and chemical constituents (Figures 2 and 3). They then combined these data with 268 previously-published data for wells in the Alluvium (n = 57), Catskill (n = 147), and Lock Haven (n = 64) aquifers 21, 22 for a total of 426 shallow groundwater samples. We analyzed major and trace element geochemistry and a broad spectrum of isotopic tracers (18O, 2H, 87Sr/86Sr, 228Ra/226Ra) in shallow ground water and compared these to published 9, 24, 25 and new data of 83 samples from underlying Appalachian brines in deeper formations from the region (Table S.2) to examine the possibility of fluid migration between the hydrocarbon producing Marcellus formation and shallow aquifers in NE PA. Integration of these geochemical tracers could delineate possible mixing between the Appalachian brines and shallow ground water.

Findings and Discussion

Based on characteristics of the water chemistry from the Alluvial, Catskill, and Lock Haven shallow aquifers there is a wide range of solute concentrations from dilute ground water. The chlorine concentrations were less than 20 mg/L and the TDS concentrations less than 500 mg/L,

7 which means PNAS was then able to divide the water samples into four types of ground water (Figure 2). Ground water types A and B (n = 118 of 158 samples from this and PNASs previous study 7 are characterized by low salinity and high Na/Cl, Br/Cl molar ratios (according to Table S.1). Water types C and D had a high salinity, meaning the concentration of chlorine was greater than 20 mg/L, and were divided further based on their Br/Cl molar ratios. Ground water type D (n = 27 of 158) was found to have a distinctively high (Figure 3) Br/Cl molar ratio (>0.001) and a low Na/Cl molar ratio (<5.0). Type C (n = 13 of 158) was found discovered to have a relatively low Br/Cl molar ratio (<0.001) and higher nitrate (NO3-) concentrations. Based on these concentrations, PNAS attributed to salinization from domestic sources such as wastewater or road salt; both typically have low Br/Cl ratios. Ground water types C and D are significantly different from the water chemistry of types A, B and C (Table S.3).

Figure 3 Generalized stratigraphic section in the subsurface of western and eastern PA plateau adapted from (17, 18, 21, 22) and Sr isotope data of Appalachian brines and type D saline groundwater. Variations of 87Sr86Sr ratios in Appalachian Brine and type-D groundwater samples show enrichment compared to the Paleozoic secular seawater curve (dashed grey line) (52). Note the overlap in values of type-D shallow ground water with 87Sr86Sr values in Marcellus brines or older formations (24, 25, 27) but no overlap with the Upper Devonian brines in stratigraphically equivalent formations (Table S.2) (24, 27).

8 In the 1980s there was a geochemical analysis of data collected 21, 22 revealed shallow salinized ground water that had higher chlorine concentrations (> 20 mg/L) and lower Na/Cl molar ratios. This saline water mimics that of ground water type D with vague (Table S.3) concentrations of major cations and anions (Figures 4A and 4B). Bromide concentrations were not available in this historical data set. PNSA assigned historical samples with chlorine concentrations and low Na/Cl ratios as possible type D samples (n = 56 of 268). The remaining historical samples were designated as possible type C samples. Because type D water samples are characterized with Na/Cl, Sr/Cl, Li/Cl, Ba/Cl and Br/Cl ratios similar to brines found in the deeper Appalachian
Figure 4. Bromide vs. chloride concentrations (log-log scale) in shallow groundwater in NE PA and Appalachian brines from this and previous studies 18, 19 . The linear relationship (type D: r2 = 0.99, p < 1 10-5; sample types AC: r2 = 0.14) between the conservative elements Br and Cl demonstrates that the majority of the higher salinity samples of type D are derived from dilution of Appalachian brines that originated from evaporated seawater. Even with a large dilution of the original brine, the geochemical signature of type-D waters are still discernable in shallow groundwater from other high salinity (Cl > 20 mg/L) groundwater with low Br/Cl ratios (type C). Type C water likely originated from shallow sources such as septic systems or road deicing. Seawater evaporation line is from 28.

formations, 7, 9, 24, 25 it is possible that there are occurrences of mixing of shallow modern water in deep formation brines. The

9 linear correlations observed for Br, Na, Sr, Li, and Ba with chloride (Figure 4 and Figure S.3 AF) demonstrate that the salinity in these shallow aquifers is most likely derived from mixing of deeper formation brines.

Figure 5. Ternary diagrams that display the relative percent of the major cations (A) and anions (B) in shallow groundwater samples from this and previous studies 21, 22. The overlap indicates that Na-Ca-Cl type saline water was present prior to the recent shale-gas development in the region and could be from natural mixing.

The stable isotopes (18O = 8 to 11; 2H = 53 to 74) of all shallow groundwater types (AD) are indistinguishable (p > 0.231) and fall along the local meteoric water line (LMWL) 26 (Figure 6). Shallow groundwater isotopic compositions do not show any positive 18O shifts towards the seawater evaporation isotopic signature as observed in the Appalachian brines. Very small contributions of brine have a large and measureable effect on the geochemistry and isotopes of dissolved salts (Figure 4) but limited effect on 18O and 2H Because of the large difference in concentrations between the brines and fresh water. Oxygen and hydrogen isotopes are not sensitive tracers for the mixing of the Appalachian brines and shallow groundwater because of the large percentage of the fresh water component in the mixing blend; mass-balance calculations indicate that only a brine fraction of higher than approximately 20% would change the 18O and 2H of salinized groundwater measurably.

10 The data presented in this study suggest that the Appalachian brines evolved by evaporation from a common seawater origin but underwent varying stages of alteration. The first stage of evolution common to all of the brines is the evaporation of seawater beyond halite saturation resulting in brines with high Br/Cl and low Na/Cl ratios relative to seawater 9. The degree of evaporation is equivalent to 2040-fold, though mixing between brines of different evaporation stages cannot be excluded. The brines then likely underwent dolomitization with carbonate rocks that enriched calcium (Ca) and depleted magnesium (Mg) in the brine relative to the seawater evaporation curve 9 (Figures S.3 B and C) and sulfate reduction that removed all sulfate. In addition, the composition of each respective hyper saline Ca-Cl Appalachian brine was differentially altered by interactions with the host aquifer rocks presumably under tectonicallyinduced thermal conditions 29 that resulted in resolvable variations in Sr/Ca, Ba/Sr, and 87Sr/86Sr ratios. The final stage of brine alteration that accounts for the observed brine compositions is dilution 9. The net results of these processes generated large variations in brine salinity relatively homogeneous elevated Br/Cl ratios and enriched 18O and 2H in all Appalachian brines. The remnant geochemical signatures of formation specific brine-rock interactions provide the most suitable basis for differentiating the Appalachian brines. The Sr/Ca ratios of the produced waters from Marcellus wells are significantly higher than brines evolved through calcite but are consistent with equilibrium with other minerals such as gypsum or celestite 30. New and compiled data presented in Table S.2 show distinctive geochemical fingerprints among the Appalachian brines in the different formations. PNAS used these variables as independent tracers to differentiate possible brine sources for the shallow type D groundwater. Brines from the Marcellus Formation show systematically low (less radiogenic) 87Sr/86Sr (0.710000.71212; n = 50) and high Sr/Ca (0.030.17) ratios compared to the more radiogenic Upper Devonian brines

11 and low Sr/Ca (0.0020.08) (Figure S.4). This geochemical proxy has the potential to elucidate regional flow paths, salinity sources and the specific source of the Appalachian brines 24, 27 (Figure 7) because of the relatively high Sr concentration and diagnostic Sr/Ca, Ba/Sr, and
87

Sr/86Sr ratios. The 87Sr/86Sr ratios of low saline groundwater (type A and B) vary widely in the

shallow aquifers, but the overwhelming majority are distinctly different from values of produced water brines from Upper Devonian 27. Conversely, the type D shallow groundwater data show a linear correlation between Sr and Cl and a decrease of 87Sr/86Sr from 0.714530.70960 with increasing Sr concentrations and salinity confirming that the resulting salinity is likely derived from mixing with Marcellus Formation brine (Figure 7).
Figure 6. 2H vs. 18O in shallow groundwater from this study and Appalachian brines. The water isotope composition of the shallow groundwater samples including the Salt Spring appear indistinguishable from each other and the local meteoric water line (LMWL) 26 and do not show any apparent trends toward the stable isotope ratios of the Appalachian brines 9, 25. The data indicate that dilution of the type-D waters likely occurred on modern (post-glacial) time scales. Symbol legend is provided in Fig. 4.

Figure 7. 87Sr/86Sr vs. Sr concentrations (log scale) of Appalachian Brines 24, 27 and shallow groundwater samples in the study area. The shallow groundwater samples are divided in the figure based on water types. Increased concentrations of Sr in the shallow aquifers are likely derived from two component mixing: (i) A low salinity, radiogenic 87Sr86Sr groundwater sourced from local aquifer reactions; and (ii) A high salinity, less radiogenic 87Sr/86Sr water consistent with Marcellus Formation brine. The Marcellus Formation 87Sr/86Sr appears lower in western Bradford than in Susquehanna and Wayne counties. Other brine sources such as the Upper Devonian formations have a more radiogenic 87 Sr/86Sr ratio that does not appear to show any relationship to the salinized shallow groundwater. Symbol legend is provided in Fig. 5.

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Conclusion
PNAS concludes that regions with the combination of deep high water pressure and enhanced natural flow paths 42, 44, 45 could induce steep hydraulic gradients. This could also allow the flow of deeper fluids to zones of lower water pressure 46, 47. The higher frequency of the saline type D water occurrence in valleys is consistent with hydrogeological modeling of regional discharge to lower water pressure in the valleys with greater connectivity to the deep subsurface 46, 47, 48. The time scale for fugitive gas contamination of shallow aquifers can be decoupled from natural brine movement specifically when gas concentrations exceed solubility (approx. 30 cckg) and forms mobile free phase gases. In western Pennsylvania, on the contamination of shallow aquifers has been described as leakage of highly pressurized gas through the over-pressurized annulus of gas wells and into the overlying freshwater aquifers via fractures and faults 46, 47.

This study shows that some areas of elevated salinity with type D composition in northeastern Pennsylvania were present prior to shale-gas development and most likely are unrelated to the most recent shale gas drilling. Because of a preexisting network of cross-formational pathways that has enhanced hydraulic connectivity to deeper geological formations, however, the coincidence of elevated salinity in shallow groundwater with a geochemical character similar to produced 46. Water from the Marcellus formation suggests that these areas could be at greater risk of contamination from shale gas development. Future research should focus on systematically monitoring these areas to test potential mechanisms of enhanced hydraulic connectivity to deeper formations, confirm the brine source, and determine the timescales for possible brine migration.

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Additional Figures and Tables

Figure S.1 Geologic map of the study area with the three major aquifers [Alluvium, Catskill (Dck), and Lock Haven (Dhl)] and samples collected during this study Other formations of Mississippian and Pennsylvanian are shown in gray. Cross section lines are approximated based on (1) and (2).
1 Osborn SG, Vengosh A, Warner NR, Jackson RB (2011) Methane contamination of drinking water accompanying gaswell drilling and hydraulic fracturing. Proc Natl Acad Sci USA 108:81728176. 2 Molofsky LJ, Connor JA, Farhat SK, Wylie AS, Jr, Wagner T (2011) Methane in Pennsylvania water wells unrelated to Marcellus shale fracturing. Oil Gas J 109:5467.

14 Figure S.2 A and B. Generalized cross sections adapted from (1) and (2) that display the relative vertical separation between the shallow aquifers (Alluvium, Catskill, and Lock Haven) and underlying formations. Note that the alluvium aquifer is not depicted nor was it included in the source for the well logs (Geological Sample Co., Farmington, NM); however, it is present and is thicker in valleys than uplands. The vertical separation between the water wells and the Marcellus formation ranges between 8002,000m with the minimum found at the apex of the anticlinal hinge displayed in S.2B. Note that these low amplitude anticline-syncline features are common in this region of the Appalachian plateau.
1 Osborn SG, Vengosh A, Warner NR, Jackson RB (2011) Methane contamination of drinking water accompanying gas-well drilling and hydraulic fracturing. Proc Natl Acad Sci USA 108:81728176. 2 Molofsky LJ, Connor JA, Farhat SK, Wylie AS, Jr, Wagner T (2011) Methane in Pennsylvania water wells unrelated to Marcellus shale fracturing. Oil Gas J 109:5467.

15 Figure S.3. Na, Ca, Mg, Sr, Ba, and Li versus Cl concentrations (loglog scale) in investigated shallow groundwater in NE PA and deep Appalachian basin brines from this and previous studies (1, 2). The linear relationship between the different elements and the conservative Cl demonstrates that the majority of the higher salinity samples of type D are derived from conservative dilution (mixing) of Appalachian brine in NE PA. Type D regression results (r2, p-value) between Cl and Ca (0.89, 2.17 1012), Mg (0.83, 2.4 1010), Sr (0.92, 4.8 1014), Na (0.94, 1.33 1015), Ba (0.92, 3.23 1014), and Li (0.96, 3.7 1017). See Fig. 3 legend for symbol description. Seawater evaporation line is adapted from (3).

1 Taylor L (1984) Groundwater Resources of the Upper Susquehanna River Basin (Water Resources Report 58, Pennsylvania) (Pennsylvania Department of Environmental ResourcesOffice of Parks and ForestryBureau of Topographic and Geologic Survey) , p 136. 2 Williams J, Taylor L, Low D (1998) Hydrogeology and Groundwater Quality of the Glaciated Valleys of Bradford, Tioga, and Potter Counties (Water Resources Report 68, Pennsylvania) (Commonwealth of Pennsylvania Department of Conservation and Natural Resources), p 89. 3 McCaffrey M, Lazar B, Holland H (1987 ) The evaporation path of seawater and the coprecipitation of Br and K with halite. J Sediment Petrol 57:928 937.

16 Figure S.4. 87Sr/86Sr vs. Sr/Ca ratios in shallow ground water samples in NE PA and Appalachian brines. The distinctive high Sr/Ca and low 87 Sr/86Sr fingerprints of the Marcellus formation brine (1) appear to control the Sr/Ca and 87Sr/86Sr variations of the saline groundwater of type D. These values are distinct from the compositions of other Appalachian Brines collected from Upper Devonian formations (Venango, Bradford sandstone, and organic-rich shales). See Fig. 4 for symbol description.
1 Chapman EC, et al. (2012) Geochemical and strontium isotope characterization of produced waters from Marcellus Shale natural gas extraction. Environ Sci Technol 46:3545 3553.

Figure S.5. 226Ra activities (pCiL) vs. total dissolved salts (TDS) in shallow groundwater and Marcellus brines (14) from NE PA. The increase of 226Ra with salinity appears consistent with conservative mixing (Type D: r2 = 0.93, p = 3.39 107) with Marcellus Formation brine from the study area. The activities of Ra in most of the shallow aquifer samples are rarely above the EPA guideline (5 pCiL). See Fig. 4 legend for symbol description.
1 Rowan E, Engle M, Kirby C, Kraemer T (2011) Radium content of oil-and gas-field produced waters in the northern Appalachian Basin (USA)Summary and discussion of data (USGS Scientific Investigations) Report 20115135, p 31. 2 Osborn SG, McIntosh JC (2010) Chemical and isotopic tracers of the contribution of microbial gas in Devonian organic-rich shales and reservoir sandstones, northern Appalachian Basin. Appl Geochem 25:456471. 3 Osborn SG, Vengosh A, Warner NR, Jackson RB (2011) Reply to Saba and Orzechowski and Schon: methane contamination of drinking water accompanying gas-well drilling and hydraulic fracturing. Proc Natl Acad Sci USA 108:E665E666. 4 Dresel P, Rose A (2010) Chemistry and origin of oil and gas well brines in western Pennsylvania: -01, p 48.