Western Kentucky University TopSCHOLAR® Masters Theses & Specialist Projects Graduate School Fall 2020 Application of Excitation-Emission Matrices to Fluorescent Dye Tracing of Groundwater Flow Cayla M. Baughn Western Kentucky University, [email protected] Follow this and additional works at: https://digitalcommons.wku.edu/theses Part of the Environmental Monitoring Commons, Hydrology Commons, and the Other Earth Sciences Commons Recommended Citation Baughn, Cayla M., "Application of Excitation-Emission Matrices to Fluorescent Dye Tracing of Groundwater Flow" (2020). Masters Theses & Specialist Projects. Paper 3227. https://digitalcommons.wku.edu/theses/3227 This Thesis is brought to you for free and open access by TopSCHOLAR®. It has been accepted for inclusion in Masters Theses & Specialist Projects by an authorized administrator of TopSCHOLAR®. For more information, please contact [email protected]. APPLICATION OF EXCITATION-EMISSION MATRICES TO FLUORESCENT DYE TRACING OF GROUNDWATER FLOW A Thesis Presented to The Faculty of the Department of Geography and Geology Western Kentucky University Bowling Green, Kentucky In Partial Fulfillment Of the Requirements for the Degree Master of Science By Cayla Baughn May 2020 APPLICATION OF EXCITATION-EMISSION MATRICES TO FLUORESCENT DYE TRACING OF GROUNDWATER FLOW Date Recommended: _________________________July 25, 2020 Digitally signed by Groves, Groves, Christopher Christopher __________________________________________Date: 2020.08.06 13:40:06 -05'00' Chris Groves, Director of Thesis Digitally signed by Patricia Patricia Kambesis Kambesis __________________________________________Date: 2020.08.06 15:26:11 -05'00' Patricia Kambesis Digitally signed by Fredrick D. Fredrick D. Siewers Siewers __________________________________________Date: 2020.08.06 15:01:31 -05'00' Fred Siewers Digitally signed by Cathleen Webb Cathleen Webb Date: 2020.08.06 16:08:59 -05'00' __________________________________________ Cathleen Webb Digitally signed by Ranjit T. Koodali Ranjit T. Koodali Date: 2020.08.06 16:20:27 -05'00' ____________________________________ Associate Provost for Research and Graduate Education ACKNOWLEDGMENTS I would first like to extend to my advisor, Dr. Chris Groves, and the Crawford Hydrology Laboratory my sincere gratitude for providing the monetary and laboratory resources necessary to facilitate the completion of this thesis and my graduate experience as a whole. I would also like to thank my thesis committee, including Drs. Groves, Patricia Kambesis, Fred Siewers, and Cate Webb, for their input through the development and completion of this thesis. I would like to personally thank Dr. May for supporting me and for all of our times joking around. Your classes were one of the best parts of my program. Autumn Turner, thank you for being such a joy to work with at CHL. I hope our paths cross often! Cesalea Osborne and Josh Allison, thank you for being the sincerest of friends ever since we first met, for always believing in me, and for your optimism. I hope your happiness knows no limits! Thank you also Colleen Hoskins and Austin Dewitz. You were true friends last summer when I worked on this research at night in the truck in Nevada and it seemed like it would never happen. I’m thankful to have you as friends even now. Finally, I would like to thank my family and Manny Jimenez for their undying love, support, patience, kindness, and unfailing sense of humor. Thank you, Mom, for always being there for me, no matter what, even when your FCA shirt is on! Thank you, Granny and Grandpa, for being the best grandparents I could ever want and for being darn good field buddies too! Thank you, Mim and Dad, for helping me keep things in perspective by being plain funny. Thank you, Scarlett, for being the sister I never had but always wanted. Finally, Manny, thank you for all this time you’ve spent with me, your love, patience, and thank you for all of our adventures. Time for the next one. iii TABLE OF CONTENTS 1. Introduction .................................................................................................................... 1 1.1 Karst Aquifer Flow Systems ................................................................................... 1 1.2 Significance and Research Objectives .................................................................... 5 2. Literature Review ........................................................................................................... 7 2.1 Fluorescent Dye Tracing Tests: Field Procedures .................................................. 7 2.2. Tracer Tests: Laboratory Experiments ................................................................. 12 2.2.1 Sample Processing and Preparation of Standard Dilutions ........................... 12 2.2.2 Analysis Using Fluorescence Spectrometry: Procedures ............................. 14 2.3 Challenges to Analytical Fluorescence Measurement in Hydrology .................... 21 2.4 Three-Dimensional Synchronous Scanning .......................................................... 26 2.5 Scattering and Red and Blue Shifts ...................................................................... 29 2.6 Research Objectives .............................................................................................. 32 3. Study Area ................................................................................................................... 33 3.1 Introduction ........................................................................................................... 33 3.2 The Lost River Groundwater Basin ...................................................................... 33 3.2.1 Physiographic Setting ................................................................................... 33 3.2.2 Hydrogeology of the Lost River Groundwater Basin ................................... 34 3.2.3 Extent of the Lost River Groundwater Basin ................................................ 35 3.2.4 Cultural and Contamination History of the Lost River Groundwater Basin 37 4. Methods........................................................................................................................ 41 4.1 Process Overview .................................................................................................. 41 iv 4.2 General Laboratory Methods ..................................................................................42 4.3 Single Standard Dilutions .......................................................................................46 4.4 Mixed Standard Dilutions .......................................................................................46 4.5 Lost River Cave Grab Samples ...............................................................................47 4.6 Two-Dimensional Synchronous Scanning ..............................................................48 4.6.1 Two-Dimensional Synchronous Scanning Parameters and Settings ..............51 4.7 Three-Dimensional Synchronous Scanning ............................................................54 4.7.1 Published Three-Dimensional Synchronous Scanning Parameters ................56 4.7.2 Three-Dimensional Synchronous Scanning Experimental Parameters ..........61 5. Results ............................................................................................................................65 5.1 Two-Dimensional Synchronous Scans of Single Dye Dilutions ............................65 5.2 Single Dye Dilution EEMs and Contour Diagrams ................................................66 5.3 Two-Dimensional Synchronous Scans of Mixed Dye Dilutions ............................71 5.4 Mixed Standard Dilution EEMs and Contour Diagrams ........................................74 5.5 Two-Dimensional Synchronous Scans of Lost River Cave Samples .....................80 5.6 Lost River Cave EEMs and Contour Diagrams ......................................................84 6. Discussion ......................................................................................................................87 6.1 Single Dye Dilution EEMs and Contour Diagrams ................................................87 6.2 Mixed Dye Dilution EEMs and Contour Diagrams ................................................91 6.2.1 FLEO 1:1 and FLEO 1:10...............................................................................92 6.2.2 FLEO 1:100 ....................................................................................................94 6.2.3 FLEO 10:1 ......................................................................................................97 6.2.4 FLEO 10:10 ..................................................................................................100 v 6.2.5 FLEO 10:100 ................................................................................................102 6.2.6 RWTSRB 1:1, RWTSRB 1:10, RWTSRB- 1:100, RWTSRB 10:1, RWTSRB 10:10, and RWTSRB 10:100 ........................................................105 6.2.7 RWTSRB 1:1 and RWTSRB 1:10 ................................................................106 6.2.8 RWTSRB 1:100 ............................................................................................106 6.2.9 RWTSRB 10:1 and RWTSRB 10:10 ............................................................108 6.2.10 RWTSRB 10:100 ........................................................................................109 6.2.11 RWTSRB 100:1 ..........................................................................................112