MINERALOGICAL AND FACIES VARIATIONS WITHIN THE UTICA SHALE, OHIO USING VISIBLE DERIVATIVE SPECTROSCOPY, PRINCIPAL COMPONENT ANALYSIS, AND MULTIVARIATE CLUSTERING by JULIE M BLOXSON Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Earth, Environmental, and Planetary Sciences CASE WESTERN RESERVE UNIVERSITY August 2017 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the thesis/dissertation of JULIE M BLOXSON candidate for the degree of Doctor of Philosophy Committee Chair Beverly Saylor Gerald Matisoff Steven Hauck Xiong Yu Jonathan Cowen June 21, 2017 ii TABLE OF CONTENTS LIST OF FIGURES.......................................................................................................................... v LIST OF TABLES .........................................................................................................................viii Abstract ...................................................................................................................................... 1 CHAPTER 1: Introduction............................................................................................................. 3 CHAPTER 2: Geologic Setting and History of the Appalachian Basin during the Middle-Late Ordovician .................................................................................................................................. 9 CHAPTER 3: Varimax-Rotated Visible Derivative Reflectance Spectroscopy of the Utica Shale/ Point Pleasant Formation in Ohio .............................................................................................. 17 Abstract .................................................................................................................................... 17 1. Introduction .......................................................................................................................... 18 2. Methods ............................................................................................................................... 24 2.1 Core Selection ............................................................................................................. 24 2.2 Visible Derivative Spectroscopy ................................................................................... 25 2.3 Principal Component Analysis with Varimax Rotation .................................................. 27 2.4 Comparative Sample Analysis ...................................................................................... 29 3. Results .................................................................................................................................. 32 3.1 Reflectance and Principal Component Analysis ............................................................ 32 3.2 Downcore Variations ................................................................................................... 46 3.3 Estimating Calcite Content ........................................................................................... 57 4. Discussion ............................................................................................................................. 60 4.1 Extracted VDS Mineralogy ........................................................................................... 60 4.2 Downcore Variations ................................................................................................... 64 4.3 Practical Applications................................................................................................... 68 5. Conclusion ............................................................................................................................ 70 CHAPTER 4: Shale and Carbonate Facies Identifications using Core Compositional Data and Geophysical Well Logs. .............................................................................................................. 70 ABSTRACT ................................................................................................................................. 71 1. Introduction .......................................................................................................................... 72 1.1 GAMLS ........................................................................................................................ 74 2. Methods ............................................................................................................................... 77 2.1 Well Data Selection and Clustering .............................................................................. 77 2.2 Estimating Missing Data............................................................................................... 82 2.3 Comparison Between Electrofacies and Lithofacies Determined on Core ..................... 83 iii 3. Results .................................................................................................................................. 84 3.1 Electrofacies ................................................................................................................ 84 3.2 Core Comparison to Electrofacies and Lithofacies Assignments ................................... 94 3.3 Lithofacies Compared to Measured Calcite Content..................................................... 99 4. Discussion ........................................................................................................................... 102 5. Conclusion .......................................................................................................................... 105 CHAPTER 5: Facies distribution within middle Upper Ordovician Strata across Ohio using core and well logging. ..................................................................................................................... 107 1. Introduction ........................................................................................................................ 108 2. Methods ............................................................................................................................. 113 3. Results ................................................................................................................................ 120 3.1 Depth and Thickness Trends ...................................................................................... 120 3.2 Facies Variations Observed by Cross Sections ............................................................ 123 3.3 Statewide Facies Variations and Depositional Influences ........................................... 128 3.3.1 Sebree Trough ........................................................................................................ 132 3.3.2 Waverly Arch .......................................................................................................... 133 3.3.3 Basement Structures .............................................................................................. 134 4. Discussion ........................................................................................................................... 134 4.1 Influence of Paleogeographic Features on Carbonate-Shale Mixing ........................... 134 4.2 Lithology Changes...................................................................................................... 137 4.3 Carbonate Concentrations in the Utica Shale Affecting CO2 Sequestration and Hydraulic Fracturing........................................................................................................................ 139 5. Conclusion .......................................................................................................................... 141 Appendix A – QXRD using RockJock for Synthetic Samples and Their Error Analysis, and Raw qXRD for Cores 2982 and 2984. ........................................................................................... 142 Appendix B - Calcite Content and GAMLS Mode Assignments for Wells 4, 32, 44, and 52. ....... 155 Appendix C - Total Carbon, Total Inorganic Carbon, Total Carbon Contents, Calculated Carbonate Contents, and Measured Carbonate Contents for Cores 1982 and 2984 .............................. 169 Appendix D - GAMLS Well numbers ........................................................................................ 170 Appendix E - Well Information Used in ArcGIS for Isopach and Structure Mapping .................. 171 Appendix F - Tops Information ................................................................................................ 178 REFERENCES……………………………………………………………………………………………………………………………184 iv LIST OF FIGURES CHAPTER 2 Figure 1. Late Ordovician paleogeography. ....................................................................10 Figure 2. Generalized stratigraphic column of Ordovician strata in Ohio ........................12 Figure 3. Eastern United States showing the extent of the Sebree Trough .....................13 CHAPTER 3 Figure 1. Extent of the Utica Shale and Point Pleasant Formation. .................................22 Figure 2. Ohio Ordovician stratigraphy showing the relative positions of cores .............23 Figure 3. QXRD example spectrum for sample 10 from core 2984 .................................31 Figure 4. Component loadings compared to known mineral standards for core 2982 ....33 Figure 5. Component loadings compared to known mineral standards for core 2984 ....35 Figure 6. Component loadings compared to known mineral standards