Washington University in St. Louis Washington University Open Scholarship Engineering and Applied Science Theses & McKelvey School of Engineering Dissertations Spring 5-15-2018 Coupling of Geochemical Reactions and Geophysical Properties of Clay Minerals in Energy- related Subsurface Engineered Systems Lijie Zhang Washington University in St. Louis Follow this and additional works at: https://openscholarship.wustl.edu/eng_etds Part of the Environmental Engineering Commons Recommended Citation Zhang, Lijie, "Coupling of Geochemical Reactions and Geophysical Properties of Clay Minerals in Energy-related Subsurface Engineered Systems" (2018). Engineering and Applied Science Theses & Dissertations. 337. https://openscholarship.wustl.edu/eng_etds/337 This Dissertation is brought to you for free and open access by the McKelvey School of Engineering at Washington University Open Scholarship. It has been accepted for inclusion in Engineering and Applied Science Theses & Dissertations by an authorized administrator of Washington University Open Scholarship. For more information, please contact [email protected]. WASHINGTON UNIVERSITY IN ST. LOUIS Department of Energy, Environmental and Chemical Engineering Dissertation Examination Committee: Young-Shin Jun, Chair Richard L. Axelbaum Randall T. Cygan John D. Fortner Daniel E. Giammar Coupling of Geochemical Reactions and Geophysical Properties of Clay Minerals in Energy- related Subsurface Engineered Systems by Lijie Zhang A dissertation presented to The Graduate School of Washington University in partial fulfillment of the requirements for the degree of Doctor of Philosophy May 2018 St. Louis, Missouri © 2018, Lijie Zhang Table of Contents List of Figures .............................................................................................................................. vii List of Tables ............................................................................................................................... xii Acknowledgments ...................................................................................................................... xiii Abstract of the Dissertation ....................................................................................................... xv Chapter 1. Introduction ............................................................................................................... 1 1.1 Background ........................................................................................................................... 1 1.1.1 Geologic CO2 Sequestration (GCS) and CO2-enhanced Unconventional Oil/Gas Recovery .................................................................................................................................. 1 1.1.2 Brine–mineral Interactions under Conditions Relevant to Subsurface Operations ........ 2 1.1.3 Importance of Coupling Geochemical Reactions and the Geophysical Properties of Minerals ................................................................................................................................... 5 1.2 Research Objectives and Tasks ............................................................................................. 7 1.2.1 Current Knowledge Gaps ............................................................................................... 7 1.2.2 Specific Objectives and Tasks ........................................................................................ 9 1.3 Dissertation Overview ......................................................................................................... 11 Chapter 2. Effects of Salinity-Induced Chemical Reactions on Biotite Wettability Changes under Geologic CO2 Sequestration Conditions ........................................................................ 15 Abstract ..................................................................................................................................... 15 2.1 Introduction ......................................................................................................................... 16 2.2 Experimental Section .......................................................................................................... 17 2.2.1 Minerals and Chemicals ............................................................................................... 17 2.2.2 High Temperature and High Pressure Batch Experiments ........................................... 18 2.2.3 Contact Angle Measurements ....................................................................................... 20 2.2.4 Characterization of Reacted Biotite .............................................................................. 21 2.3 Results and Discussion ........................................................................................................ 22 2.3.1 Higher Salinity Enhances Biotite Dissolution .............................................................. 22 2.3.2 Chemical Reactions Make Biotite Surfaces More Hydrophilic ................................... 25 2.3.3 Reacted Biotite Surfaces Exhibit a Lower CO2 Adhesion and Contact Angle Hysteresis ............................................................................................................................................... 28 2.4 Environmental Implications ................................................................................................ 31 Acknowledgments ..................................................................................................................... 33 ii Supporting Information for Chapter 2 ....................................................................................... 34 Chapter 3. Distinctive Reactivities at Biotite Edge and Basal Planes in the Presence of Organic Ligands: Implications for Organic-Rich Geologic CO2 Sequestration ................... 42 Abstract ..................................................................................................................................... 42 3.1 Introduction ......................................................................................................................... 43 3.2 Experimental Section .......................................................................................................... 47 3.2.1 Chemicals and Mineral Sample Preparation ................................................................ 47 3.2.2 High Temperature and High Pressure Dissolution Experiments .................................. 48 3.2.3 Analyses of Surface Morphological Changes .............................................................. 50 3.2.4 Identification of Secondary Mineral Phases ................................................................. 50 3.2.5 Fourier Transform Infrared (FTIR) Spectroscopy Analyses ........................................ 51 3.3 Results ................................................................................................................................. 52 3.3.1 Enhanced Biotite Dissolution by Oxalate and Inhibited Dissolution by Acetate ......... 52 3.3.2 Effects of Acetate and Oxalate on Biotite’s Surface Morphological Changes ............. 54 3.3.3 Biotite Anisotropic Dissolution .................................................................................... 57 3.3.4 Precipitation of Secondary Minerals on Basal surfaces and Edge Surfaces................. 59 3.4 Discussion ........................................................................................................................... 60 3.4.1 Interactions between Acetate and Biotite: pH-induced Mechanisms ........................... 60 3.4.2 Interactions between Oxalate and Biotite: Surface Complexation ............................... 62 3.4.3 Distinctive Reactivities at Biotite Edge and Basal Surfaces ........................................ 65 3.5 Environmental Implications ................................................................................................ 66 Acknowledgments ..................................................................................................................... 67 Supporting Information for Chapter 3 ....................................................................................... 68 Chapter 4. Effects of Phosphate on Biotite Dissolution and Secondary Precipitation under Conditions Relevant to Engineered Subsurface Systems ........................................................ 80 Abstract ..................................................................................................................................... 80 4.1 Introduction ......................................................................................................................... 81 4.2 Experimental Section .......................................................................................................... 85 4.2.1 Minerals and Chemicals ............................................................................................... 85 4.2.2 High Temperature and High Pressure Reactions .......................................................... 86 4.2.3 Characterization of Reacted Biotite Samples ............................................................... 87 4.2.4 Fourier Transform Infrared (FTIR) Spectroscopy Analyses of Phosphate Complexation ............................................................................................................................................... 90 4.3 Results and Discussion .......................................................................................................