Acknowledgements I would like to thank the following people and departments for their assistance in making this project possible. This research was partially funded by the Otsego County Conservation Association through Scott Fickbohm at the Otsego County Soil and Water Conservation District. Other funding came from the Departments of Chemistry, and Geology and Environmental Sciences at Hartwick College. I thank Dr. John Dudek, who assisted me with instrumentation throughout my analytical work and Dr. Zsuzsanna Balogh-Brunstad, who served as a mentor and thesis advisor for this project. ii Baseline Water Quality Monitoring in the Watersheds of Otsego County, NY by Nicole M. Daniels, B.A. Hartwick College May 2013 Advisor: Dr. Zsuzsanna Balogh-Brunstad Abstract The Marcellus Shale has become of particular interest to those interested in natural gas production using the now economically feasible hydraulic fracturing (fracking) technique. The Otsego County Soil and Water Conservation District has begun monitoring local watersheds so that a baseline for various parameters (pH, turbidity, total dissolved solid, temperature, and electrical conductivity) can be set. This way, if the Marcellus Shale in New York State is selected for natural gas extraction using hydraulic fracturing methods, the water quality can be compared to pre-gas extraction levels to insure the integrity of the water quality and ecosystem. The goal of this study was to determine the current concentrations of strontium in surface water in Otsego County, NY as it is an indicator of brine water input to freshwater ecosystems. Brines are associated with flowback and production waters of natural gas extraction after fracking operations, and thus, can indicate a mishandling of such fluids on the surface. Additional goals of this study included monitoring of field parameters and anion content of the collected samples. Surface water samples were collected every three to four weeks for five months among 47 sites in Otsego County. These samples were filtered, preserved, and then analyzed for anion content using ion-chromatography, and strontium concentration using atomic absorption spectroscopy. We found that the watersheds are clean and strontium concentrations (averaged by sub- watersheds) range from 28.4 to 320. ppb between September 2012 and January 2013. iii TABLE OF CONTENTS Page ACKNOWLEDGEMENTS ................................................................................................ ii Abstract ....................................................................................................................... iii Introduction .............................................................................................................1 Geological Background .................................................................................................2 Water Chemistry ............................................................................................................4 Hydraulic Fracturing ......................................................................................................5 Why Strontium? .............................................................................................................7 Methods ..........................................................................................................................8 Field Sampling ...............................................................................................................8 Laboratory Preparation ................................................................................................11 Analytical Instruments .................................................................................................12 Data Analysis and Interpretation .................................................................................16 Laboratory Safety.........................................................................................................18 Field Safety ..................................................................................................................19 RESULTS ..........................................................................................................................19 Field Parameters...........................................................................................................19 Anions ..........................................................................................................................20 Strontium......................................................................................................................23 DISCUSSION ....................................................................................................................23 Field Parameters...........................................................................................................23 Anions ..........................................................................................................................25 Strontium......................................................................................................................28 iv Relationship between Sr2+ and Field Parameters .........................................................29 SUMMARY AND CONCLUSIONS ................................................................................30 REFERENCES ..................................................................................................................31 APPENDIX A. Chemical Composition of Fracking Fluids ..............................................36 APPENDIX B. Operational Instructions of Instruments ...................................................37 APPENDIX C. Hazards Associated with Utilized Chemicals ...........................................47 APPENDIX D. Chemistry Department Safety Policy .........................................................48 APPENDIX E. Department of Geology and Environmental Sciences Safety Policy ............55 APPENDIX F. Tabulated Results – Field Parameters .........................................................61 APPENDIX G. Tabulated Results – Anions .......................................................................65 APPENDIX H. Tabulated Results – Strontium ...................................................................73 APPENDIX I. Sampling Site Locations ..............................................................................79 APPENDIX J. Additional Figures ......................................................................................81 v IntroductioN The Marcellus Shale has become of particular interest to those interested in shale gas exploration and natural gas production because the hydraulic fracturing (fracking) technique became an economically feasible method of increased gas extraction and the Marcellus Shale contains a large amount of natural gas, i.e. methane. The Otsego County Soil and Water Conservation District has begun monitoring local watersheds so that a baseline for various parameters (temperature, pH, turbidity, total dissolved solids, and electrical conductivity) can be determined. This way, if the Marcellus Shale in New York State is selected for natural gas extraction using hydraulic fracturing methods, the water quality can be compared to pre-gas industry levels to insure the integrity of the water quality and ecosystem and to intervene in a timely manner if problems arise. This study is a continuation of the water quality monitoring work done by the Otsego County Soil and Water Conservation District with added parameters. The overall goal of this study was to contribute to the general monitoring efforts of the water quality in Otsego County, NY (the Upper Susquehanna River Basin). The specific interests of this study were the determination of 1) the current strontium (Sr2+) concentrations in surface water, as it is an indicator of brine water input from mishandling of flowback and/or production waters after fracking operations; and 2) the current anion content of surface waters. In addition, field parameters were monitored and recorded. Surface water samples from forty seven sites in Otsego County were collected approximately every three to four weeks for five months and field parameters were measured on- site. The collected samples were filtered, preserved, and then analyzed for anion and strontium concentrations using ion chromatography and atomic absorption spectroscopy, respectively. 1 Geological Background The Marcellus Shale is a Middle Devonian age (416-359.2 Million years), black, low density, organic rich shale that lies under most of New York, Pennsylvania, West Virginia and Ohio State (1 mile or more depth, in Otsego County), covering an area of 95,000 mi2 (Kargbo et al., 2010). Below the Marcellus Shale (2,500-7,000 feet) is the older Utica Shale (Kargbo et al., 2010). Recent data suggests that there could be as large as 439 trillion cubic feet of recoverable Marcellus Shale reserves, making it the most expansive shale gas area in the U.S.; thus, interesting the energy industry (Kargbo et al., 2010). During shale formation, small grains (mud) accumulate, and then pressurized compaction causes the layers to flatten and form thin laminar bedding, which lithifies into shale rock (Kargbo et al., 2010). Shale is different from mudstone because it is finely laminated and it splits easily along the laminations (Kargbo et al., 2010). When the organic materials in these deposits degrade anaerobically natural gas can form (Kargbo et al., 2010). The Marcellus Shale