Summary of water quality observations/challenges in Shale Gas Development

1. Summary of water quality observations/challenges in Shale Gas Development Bob Hendricks: Appalachia Groundwater Protection Lead Shell Water Team Lead UAU Marcellus Shale Coalition Shale Network 2014 Workshop May 12 and 13, 2014 Atherton Hotel (State College PA) and Willard Building (PSU)

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3. Presentation Overview • Water Quality Investigations • Regulatory and/or Water Complaint Response • Scientific Studies/Evaluations • Collaboration • Types of Data for Evaluating Water Quality • Data Evaluation Challenges • Lines of Evidence for Evaluating Potential Water Impacts • Produced/Flowback Water • Gas Migration

4. Primary Types of Data For Evaluating Water Quality • Groundwater • Pre Drill • Post Drill • Water Complaint/Response • Investigation • Produced/Flowback Wastewater • Waste Characterization • Investigation/Assessment • Gas • Production • Isotube Samples

5. Summary of Key Data Evaluation Challenges • Determination of “Changed Condition” • Natural Variability in Water Quality • Seasonal • Weather Dependent • Water Use • Water Well Construction/Water Sources • Sampling and Analyses of Methane • Presence of Pre Existing Methane • Restricted Groundwater Flow Zone Chemistry • Variability within Appalachian Basin • Data Confidentiality

6. Water Source sampling considerations • Surface Casing Installation • Multiple water bearing zones • Well Deepening for Storage • Water Usage At Time of Sampling • Well Maintenance

7. Turbidity vs. Water level change

8. Iron concentrations by sample date for daily samples Wells #1 to #7 (Nearby) 2 orders of Magnitude Change Reference: GES, SAIC, Chesapeake Presentation

9. Strontium Concentrations by Sample Date Change from 3-15 mg/l in 2 days Reference: GES, SAIC, Chesapeake Presentation

10. Headspace methane vs. water level change in 6 hours Water level drop; Headspace increase

11. Changes in dissolved methane in groundwater at “medium” (5-15 mg/L) level locations KB: (5 mg/l – 21 mg/l) EH: (ND – 14 mg/l)

12. compositions of water Types – Restricted Flow Zone 400 – 6100 (7800) 10 – 235 (330) 90 – 2,000 (2,500) 125 – 3,500 (4,600) 0.14 – 80 (1,600) 0.5 – 98 (36)

13. Piper Diagram – General Water Quality Produced Water (NaCaCl type water) Predrill Groundwater >250 ppmCl- (NaCaCl type water) Predrill Groundwater <25 ppmCl- (CaHCO3 type water) Similar to Williams, 1998 findings on water quality types in Tioga County

14. Pre-Drill – CHLORIDE vs. Well depth Higher salinity groundwater can occur at variable depths for different reasons

15. Multiple Lines of Evidence for Addressing Challenges • Data evaluation process must consider various parameters • Evaluation of potential impacts from produced/flowback water • Plot of isotope of water using meteoric water line data for comparison: 18Oversus 2H • Radium isotopes: Ra-228/Ra-226 • Stable strontium isotopes: 87Sr/86Sr • % Modern carbon (14C) in dissolved inorganic carbon (DIC) • Stable 13Cof dissolved inorganic carbon (DIC) • Evaluation of potential impacts from gas migration incidents • Methane/Ethane Ratio • Isotopic Signatures • Isotopic Reversals

16. isotopic distribution OF2H and 18O IN SURFACE WATERS - US The Global Meteoric Water Line is an equation that states the average relationship between hydrogen and oxygen isotope ratios in natural terrestrial waters, expressed as a worldwide average. Meteoric groundwater is derived from rainfall and infiltration within the normal hydrological cycle. It is generated from sea water by evaporation and deposition Groundwater originating as sea water and entrapped in the pores of marine sediments since their time of deposition is referred to as connate water. This is saline water encountered at great depths in old sedimentary formations. It is groundwater that has been removed from atmospheric circulation for a significant period of geological time. Reference: “Distribution of oxygen-18 and deuterium in river waters across the United States”, Carol Kendall and Tyler B. Coplen; US Geological Survey, Menlo Park, CA 94025, USAUS Geological Survey, Reston VA 20192, USA HYDROLOGICAL PROCESSES, Hydrol. Process. 15, 1363–1393 (2001)

17. PA Local Meteoric Water Line Local Meteoric Water Line Brine Data: Dresel P., Rose A. (2010); "Chemistry and Origin of Oil and Gas Well Brines in Western Pennsylvania", PA Geological Survey, Open-File Report OFOG 10-01.0 Well Water Data (<250ft): "Natural Gases in Ground Water near Tioga Junction, Tioga County, North-Central Junction, Tioga County, North-Central Pennsylvania—Occurrence and Use of Isotopes to Determine Origins", 2005, U.S. Department of the Interior, U.S. Geological Survey, Scientific Investigations Report 2007-5085, Table 5 (In cooperation with the Pennsylvania Department of Environmental Protection) Surface Water Data: Coplen TB, Kendall C (2000); "Stable Hydrogen and Oxygen Isotope Ratios for Selected Sites of the U.S. Geological Survey’s NASQAN and Benchmark Surface-water Networks", USGS, Open-File Report 00-160 Restricted and unrestricted GW samples plot on line

18. Radio-isotope Evaluation – Radium 228/226 ratio 18 • USGS 2001 Study: Ra-228/Ra-226 ratios in produced water from the Marcellus Shale are most commonly less than 0.3 (median 0.16), and samples from non-Marcellus reservoirs generally have Ra-228/Ra-226 ratios greater than1 (median 1.1). (Rowan et.al,, USGS Scientific Investigations Report 2011–5135, 2010) • Water Well Investigation • Well - Ra-228/Ra-226: • 2.09 pCi/l/2.32 pCi/l = 0.90 • Background in Tioga County Water Wells (USGS Study) • Well 486: Ra-228 (1.7 pCi/l) and Ra-226 (1.4 pCi/l) = 1.21 • Well 498: Ra-228 (13 pCi/l) and Ra-226 (17 pCi/l) = 0.76 • Flow back/Produced Water from Shell Marcellus Operations • Ra 228/Ra 226 – < 0.1

19. Strontium Isotopes: 87Sr/86Sr Water Well Produced Water -1 Produced Water -1 (Duplicate) Produced Water -2 Normalized to Seawater The well water has a much higher normalized strontium isotopic value than the produced water supporting different water origins. The normalized values are also different for other PA counties (10 to 45).

20. 14CDIC pmC versus 13CDIC‰ PDB in Water Samples • More modern carbon is expected in domestic wells that have surface recharge. Produced water is commonly millions of years old and should have low to no 14C (half-life of 5,730 years). • Surface and shallow groundwater tend to be lsotopically lighter in DIC as compared to formation brines and produced water High pmC and negative13 C values in near surface groundwater Depleted/absence of pmC and heavily enriched 13 C values in the produced water 14CDIC pmC 13CDIC‰ PDB

21. Methane to ethane ratio vs. 13C-methane • Predrill water sources: >1000 • Production gas: <100

22. Fingerprinting isotopes: 13C and 2 h of methane

23. Isotope reversal – regional differences Western PA Northeastern PA Vertical Depth Lateral after ~5000 ft Lateral Production Gas: > ~4500 to 5500 ft No reversal in the Marcellus Reversal in the Marcellus