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 by 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 ii 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 iv 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 v 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 vi 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 vii 14. SALT CONTAMINATED: NUMBER OF SAMPLES, DETECTIONS, AND