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AIR EMISSIONS from NATURAL GAS EXPLORATION and MINING in the BARNETT SHALE GEOLOGIC RESERVOIR by ALISA LARRAINE RICH Presented

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AIR EMISSIONS from NATURAL GAS EXPLORATION and MINING in the BARNETT SHALE GEOLOGIC RESERVOIR by ALISA LARRAINE RICH Presented AIR EMISSIONS FROM NATURAL GAS EXPLORATION AND MINING IN THE BARNETT SHALE GEOLOGIC RESERVOIR by ALISA LARRAINE RICH Presented to the Faculty of the Graduate School of The University of Texas at Arlington in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY THE UNIVERSITY OF TEXAS AT ARLINGTON May 2011 Copyright © by Alisa Larraine Rich 2011 All Rights Reserved DEDICATION I dedicate this study to the children of the Energy Revolution and to those who have come have come before me and those who will come after me. The Prophecy of the Seventh Generation is on the horizon and the Ten Indian Commandments will be your guide. Always remember, “We do not inherit the Earth from our Ancestors, we borrow it from our children.” —Native American Proverb ACKNOWLEDGEMENTS In acknowledgement of their contribution and assistance on this study I would like to thank all the members of my committee. Professors, your contribution will be remembered for my lifetime. Dr. Melanie Sattler, quiet and brilliant, has amazed me with her sincere commitment to the environment and to our field of science. I am honored to have had the opportunity to study under her. Dr. James Grover, who initially intimidated the daylights out of me, provided depth of knowledge and expertise that was critical for a successful study. His time and assistance is gratefully appreciated. Dr. Andrew Hunt, whom I have come to know well and look forward to many years of working together on particulate matter. Dr. John Holbrook, your knowledge of the industry has been particularly helpful and I have been inspired to reach further in my understanding of earth’s processes. Dr. Jeff Howard, your work is just beginning in the area of planning. I trust with your knowledge and understanding you will take your career to unlimited heights. You were all chosen, not because you are easy on doctoral candidates, quite the opposite. You were chosen because you would not allow anything less than quality to leave your offices. I wish to thank my parents, who taught me to be aware of the environment and to respect Mother Earth. For without her, we are nothing. To my children, all six of them: Sophia, David, Nikolai thank you for understanding that sometimes commitment to the greater good must come before the individual. Nicholas, Tanner and Sam, thank you for allowing me to participate in your lives. To all my kids, you make me proud; but never forget the importance of taking care of the environment. As Great Gramma Ruby would say, “…Or, I will haunt you from the grave,” God bless her soul, you know I will. To my sister, if I had designed the perfect sister, I could not have made you any better. I look forward to days of shopping ahead of us. To my husband, my friend, my strength, thanks will never be enough. I look forward to growing young iv with you and making up for lost time. Thank you for standing by me and for your encouragement. I am honored to call you my best friend. April 1, 2011 v ABSTRACT AIR EMISSIONS FROM NATURAL GAS EXPLORATION AND MINING IN THE BARNETT SHALE GEOLOGIC RESERVOIR Alisa Larraine Rich, PhD The University of Texas at Arlington, 2011 Supervising Professor: Dr. Melanie Sattler This study evaluates air emissions from natural gas mining and production in the Barnett Shale within the Dallas/Fort Worth Metroplex. Due to advances in horizontal drilling and hydraulic fracturing, natural gas production in the Barnett Shale increased from 3 wells in 2000 to almost 8,000 wells in six Metroplex counties by 2008. Currently, information regarding emissions from natural gas production, particularly regarding hazardous air pollutants, is lacking; this information is particularly important given that drilling and production is occurring in highly urbanized areas. The objectives of this study were thus: • To identify the ‘fingerprint’ of chemicals associated with natural gas production in the Barnett Shale through passive air monitoring; and • To correlate the presence of the fingerprint chemicals to methane and to each other. Air sampling was conducted at 36 sampling sites in 6 counties, resulting in 50 sets of monitoring data for subsequent statistical analysis. Passive samples were collected using summa canisters with 24-hour flow valves according to ASTM Method D-1357. Canister vi contents were analyzed for Toxic Organics (TO-14A), Tentatively Identified Compounds (TICs) and Light Hydrocarbons by Gas Chromatography/Mass Spectrometer Analysis (GC-MS). Statistical analysis confirmed a statistically significant probability that other chemicals will be present with methane including toluene, m&p xylenes, dichlorodifluoromethane, benzene, o-xylene, chloromethane, ethylbenzene, C12hydrocarbon, 1,2,3-trimethylbenzene and carbon disulfide. A Pearson’s correlation coefficient identified strong relationships between toluene and m&p xylene (r = 0.85), benzene and toluene (r = 0.89), benzene and xylene (r = 0.86). A Principal Component Analysis (PCA) identified specific chemicals associated with 2 significant factors. These factors were strongly associated to specific natural gas mining and production processes, including fracking, flaring, venting, compression, and tanks holding produced water/condensate, and injection of produced water into wells. An ANOVA F-test confirmed a significant difference of specific chemicals related to compression with a p-value of >0.05. Many of the chemicals identified in this study are hazardous air pollutants (HAPs), and are known/suspected carcinogens, mutagens, developmental toxicants and neurotoxicants. Thus, use of dispersion modeling is advisable to develop safe setback distances between natural gas drilling/production facilities and critical receptors, such as schools. vii TABLE OF CONTENTS DEDICATION ........................................................................................................................ iii ACKNOWLEDGEMENTS ..................................................................................................... iv ABSTRACT ........................................................................................................................... vi LIST OF ILLUSTRATIONS.................................................................................................... xii Chapter 1. INTRODUCTION .................................................................................................. 1 1.1 Air Pollutants from Natural Gas Production in the Barnett Shale ..................................................................................................... 1 1.1.2 Study Objective .................................................................... 3 1.1.3 Overview of Dissertation Organization ................................. 4 2. BACKGROUND .................................................................................................... 5 2.1 History and Geology of the Barnett Shale ............................................ 5 2.1.1 Geologic Timescale of the Barnett Shale ............................. 6 2.1.2 Basins of the Barnett Shale .................................................. 7 2.1.3 Barnett Shale: Conventional Versus Unconventional Deposits ................................................................................ 9 2.2 Horizontal Drilling and High-Volume Slick Water Hydraulic Fracturing .............................................................................................. 10 2.3 Stages of Development in Natural Gas Extraction and Production ............................................................................................. 12 2.3.1 Extraction Process ............................................................... 12 2.3.2 Processing and Compression of Natural Gas ...................... 14 2.3.3 Sources of Emissions from Natural Gas Extraction and Processing ..................................................................... 16 2.4 Geologic Characteristic Determinants of Hydrocarbon Deposits in the Newark East Field ........................................................ 16 2.4.1 Total Organic Carbon ........................................................... 17 2.4.2 Thermal Maturity................................................................... 17 viii 2.4.3 Production of Aliphatic and Aromatic Compounds and Thermal Maturation ....................................................... 18 2.4.4 Vitrinite Reflectance ............................................................. 19 2.4.5 Wet Gas Versus Dry Natural Gas ........................................ 21 2.4.6 Sweet Versus Sour Gas ....................................................... 23 2.4.7 Associated Versus Non-associated Gas .............................. 24 2.5 Environmental Impacts of Natural Gas Extraction and Processing ............................................................................................ 24 2.5.1 Air Emissions from Natural Gas Extraction and Processing ............................................................................ 25 2.6 Study Objectives ................................................................................... 27 3. METHODOLOGY ................................................................................................. 28 3.1 Study Question ..................................................................................... 28 3.2 Ambient Air Monitoring ......................................................................... 28 3.3 Ambient Air Monitoring Database ......................................................... 36
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