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Isotopic and Geochemical Tracers of Groundwater Flow in the Shivwits Plateau, Grand Canyon National Park

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Isotopic and Geochemical Tracers of Groundwater Flow in the Shivwits Plateau, Grand Canyon National Park University of Kentucky UKnowledge Theses and Dissertations--Earth and Environmental Sciences Earth and Environmental Sciences 2020 ISOTOPIC AND GEOCHEMICAL TRACERS OF GROUNDWATER FLOW IN THE SHIVWITS PLATEAU, GRAND CANYON NATIONAL PARK Jonathan W. Wilson University of Kentucky, [email protected] Author ORCID Identifier: https://orcid.org/0000-0002-2341-8886 Digital Object Identifier: https://doi.org/10.13023/etd.2020.488 Right click to open a feedback form in a new tab to let us know how this document benefits ou.y Recommended Citation Wilson, Jonathan W., "ISOTOPIC AND GEOCHEMICAL TRACERS OF GROUNDWATER FLOW IN THE SHIVWITS PLATEAU, GRAND CANYON NATIONAL PARK" (2020). Theses and Dissertations--Earth and Environmental Sciences. 85. https://uknowledge.uky.edu/ees_etds/85 This Master's Thesis is brought to you for free and open access by the Earth and Environmental Sciences at UKnowledge. It has been accepted for inclusion in Theses and Dissertations--Earth and Environmental Sciences by an authorized administrator of UKnowledge. For more information, please contact [email protected]. STUDENT AGREEMENT: I represent that my thesis or dissertation and abstract are my original work. Proper attribution has been given to all outside sources. I understand that I am solely responsible for obtaining any needed copyright permissions. I have obtained needed written permission statement(s) from the owner(s) of each third-party copyrighted matter to be included in my work, allowing electronic distribution (if such use is not permitted by the fair use doctrine) which will be submitted to UKnowledge as Additional File. I hereby grant to The University of Kentucky and its agents the irrevocable, non-exclusive, and royalty-free license to archive and make accessible my work in whole or in part in all forms of media, now or hereafter known. I agree that the document mentioned above may be made available immediately for worldwide access unless an embargo applies. I retain all other ownership rights to the copyright of my work. I also retain the right to use in future works (such as articles or books) all or part of my work. I understand that I am free to register the copyright to my work. REVIEW, APPROVAL AND ACCEPTANCE The document mentioned above has been reviewed and accepted by the student’s advisor, on behalf of the advisory committee, and by the Director of Graduate Studies (DGS), on behalf of the program; we verify that this is the final, approved version of the student’s thesis including all changes required by the advisory committee. The undersigned agree to abide by the statements above. Jonathan W. Wilson, Student Dr. Andrea M. Erhardt, Major Professor Dr. Michael M. McGlue, Director of Graduate Studies ISOTOPIC AND GEOCHEMICAL TRACERS OF GROUNDWATER FLOW IN THE SHIVWITS PLATEAU, GRAND CANYON NATIONAL PARK THESIS A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in the College of Arts and Sciences at the University of Kentucky By Jonathan W. Wilson Lexington, KY Co-Directors: Dr. Andrea M. Erhardt, Assistant Professor, Earth and Environmental Sciences Dr. Benjamin Tobin, Hydrogeologist, Kentucky Geological Survey Lexington, KY 2020 Copyright © Jonathan W. Wilson 2020 https://orcid.org/0000-0002-2341-8886 ABSTRACT OF THESIS ISOTOPIC AND GEOCHEMICAL TRACERS OF GROUNDWATER FLOW IN THE SHIVWITS PLATEAU, GRAND CANYON NATIONAL PARK As the impacts of global climate change on water resources continue to become more apparent, proper understanding and management of groundwater resources will be needed as supplies become more strained. Traditional methods of characterizing groundwater systems are time-intensive, costly, and can be difficult to complete in remote areas. Using ambient geochemical tracers from discrete sampling could aid in characterizing spring systems through determining flow paths, recharge areas, and carbon cycling. However, using discrete seasonal samples to understand the hydrogeology of complex, mixed-lithology aquifers has not been extensively examined. Here we explore using δ13C of dissolved organic carbon (DOC), δ13C of dissolved inorganic carbon (DIC) and fluorescent dissolved organic matter (fDOM), together with water isotopes, major ions, and geochemical modeling, to characterize springs of the Shivwits Plateau in Grand Canyon National Park. Values of carbon isotopes and fDOM for all springs reflect source values for regional surface vegetation and heterotrophic degradation of terrestrial DOM. Principal component analyses show that springs can be grouped into four groups by geochemical variability: 1) a shallow epikarst system, 2) a flow path through gypsiferous beds of the Toroweap Formation on the eastern side of the plateau, 3) a short, canyon slope runoff-dominated flow path through the Supai Group, and 4) a deeper complex flow system in the Redwall Limestone with characteristics of all other flow systems, which indicates mixing. Results show that the methods used can provide a simple conceptual model of a complex groundwater system, but higher–resolution spatial and temporal data are needed to fully understand changes resulting from changing climate. As appropriations from the Colorado River already exceed its annual streamflow and the regional climate is predicted to become more arid, characterizing groundwater resources for water supply will be paramount for the region as well as in other areas that will experience similar transitions. KEYWORDS: Hydrogeology, stable isotope, geochemistry, Grand Canyon, springs __________________________________Jonathan W. Wilson ________________________23 November 2020__________ ISOTOPIC AND GEOCHEMICAL TRACERS OF GROUNDWATER FLOW IN THE SHIVWITS PLATEAU, GRAND CANYON NATIONAL PARK By Jonathan W. Wilson __________________________________Andrea Erhardt Co-Director of Thesis __________________________________Benjamin Tobin Co-Director of Thesis __________________________________Michael M. McGlue Director of Graduate Studies __________________________________23 November 2020 Date ACKNOWLEDGMENTS I would like to thank my advisors Dr. Andrea Erhardt and Dr. Benjamin Tobin, and committee member Dr. Alan Fryar for the opportunity to conduct this research and for their assistance, guidance, and support throughout the completion of this thesis. Dr. Erhardt initiated my interest in stable isotope geochemistry and has provided amazing guidance and support throughout my academic career and helped me grow as a geochemist. Dr. Tobin provided me with the chance to work with him on an amazing project and provided invaluable guidance and assistance in field work and feedback for this thesis and comments on other writings. Finally, Dr. Fryar provided ideas for analyses and exceptional feedback for the thesis. The faculty and students of the Department of Earth and Environmental Sciences all provided support throughout my time with the department. I would like to thank Dr. Jordon Munizzi and the whole of the Kentucky Stable Isotope Geochemistry Laboratory for the extremely helpful assistance in geochemical analyses and method development for this thesis. Pete Idstein provided assistance whenever needed for field or laboratory equipment and Adrianne Gilley for all things logistical with departmental management. Finally, this research would not have been possible without the assistance in field work from Stefan Christie, Nicholas Steele, Natalie Jones, Adam Nolte, Vanessa Fichtner, Sarah Arpin, Hannah Chambless, Matt and Saj Zappitello, Andres Hernandez, Dr. Gina Lukoczki, and others who assisted. iii TABLE OF CONTENTS ACKNOWLEDGMENTS ................................................................................................. iii LIST OF TABLES ............................................................................................................. vi LIST OF FIGURES .......................................................................................................... vii CHAPTER ONE: INTRODUCTION ................................................................................. 1 1.1 Background ............................................................................................................... 1 1.2 Study area .................................................................................................................. 5 1.3 Hydrogeologic setting ............................................................................................... 7 13 13 1.4 δ CDIC and δ CDOC as tracers ................................................................................ 11 CHAPTER TWO: METHODS ......................................................................................... 14 2.1 Sample collection .................................................................................................... 14 2.2 Stable isotope analyses ............................................................................................ 15 2.2.1 δ2H and δ18O ..................................................................................................... 15 2.2.2 δ13C of soil samples .......................................................................................... 16 2.2.3 δ13C and δ18O of carbonate in rock samples ..................................................... 17 2.2.4 δ13C of dissolved inorganic carbon in spring samples ...................................... 18 2.2.5 δ13C of dissolved organic carbon in spring samples ......................................... 19 2.3 DOM absorbance and fluorescence analyses
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