Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2011 Characterization of Arsenic Upon Liming and Formation of Residual NAPL in the Vadose Zone Nabanita Raha Das Follow this and additional works at the FSU Digital Library. For more information, please contact [email protected] THE FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES CHARACTERIZATION OF ARSENIC UPON LIMING AND FORMATION OF RESIDUAL NAPL IN THE VADOSE ZONE By NABANITA RAHA DAS A Dissertation submitted to the Department of Earth, Ocean and Atmospheric Science in partial fulfillment of the requirements for the degree of Doctor of Philosophy Degree Awarded: Fall Semester, 2011 Nabanita Raha Das defended this dissertation on August 3, 2011. The members of the supervisory committee were: Lynn Dudley Professor Directing Dissertation Ruby Krishnamurti University Representative Ming Ye Committee Member James F. Tull Committee Member The Graduate School has verified and approved the above-named committee members, and certifies that the dissertation has been approved in accordance with university requirements. ii This is dedicated to, My Family. Especially to Daddy and Ma, who sacrificed many of their dreams to realize mine; and to, My husband, who supported and patiently waited for me to accomplish my dream. iii ACKNOWLEDGEMENTS I came to USA with many dreams and hopes. Some of them fell through, I had to work really hard to achieve some of them, and in the process some of them came along. But looking back, it was worth the effort. First of all, I would like to thank my advisor Dr. Lynn Dudley, without whose constant support and encouragement this would have been impossible. His remarkable patience and ability to listen when I was nervous kept me going. I would also like to thank my committee members for sharing their expertise with me and for encouraging from me time to time. Their support and comments were invaluable during this journey. Special thanks to Dr. James Tull and Dr. LeRoy Odom. You both are my favorite; thank you for those light moments when it seemed the sky was falling. I would like to thank the Banks family for ‘Joseph Bank award’ and the Buie family ‘Buie fund award’ which helped me immensely and supported my research. I would like to thank all my friends, who patiently listened to me when I was frustrated, and looked out for me when I needed, especially, Raman Rana, David Wagner, Priyashree Roy, Sambuddha Misra, Sanhita Ghosh and Suvadip Das. No word is enough to thank you all. Thank you for food, rides to the airport, taking care of my dog Zara when I was in lab for long hours and for everything else. I would also like to thank Reshmi Das, Haitham Baggazi and his family for giving me a family here in USA. I would also like to thank Pallov Pal, without whose guidance and help, my journey to USA would have been impossible. I would like to thank, Han Xue, for helping me in the lab. I would also like to remember my childhood friend Rupali Goswami (1981-2009). I wish I could talk to you one last time. May you rest in peace Munukon. I will miss you forever. I would like to thank my family and my extended family for all their support and love. Daddy and Ma, after 29 years of my life, I find myself at a place where I look back and realize what a journey it might have been for you. With three kids like us, we made your job tougher. Thank you for giving me superior value in my life. I hope I did make you proud. I would like to take this opportunity to tell you, I love you and thank you for all your support and love. iv Bhai and Dia, thank you for being there for me, through all your own troubles. I miss being there with you. I love you both. Baba and Ma, thank you for being with me through this long journey and for your countless blessings. Thank you, Didi, Rick and my little nephew Romir. You all have a very special place in my life and I love you all. Last but not the least I would like to thank my husband Rajarshi Das. Joy, I cannot thank you enough, for all the patience and support that you offered. Thank you for putting up with the 4 long years of long distance relationship. Thank you so much for all the help you provided, whether it be related to academics or personal matters. I am so lucky to have you in my life. Thank you for standing by me when the world looked away, thank you for being there and tolerating me, when I was not so pleasant to talk to and when I would behave like a nincompoop. Thank you for adopting our crazy dog Zara and taking care of her. I love you and couldn’t have done it without you. Thank you god! For helping me through this difficult time of my life. v TABLE OF CONTENTS 
 Acknowledgements ........................................................................................................................ iv
 Table of Contents ........................................................................................................................... vi
 List of Tables ............................................................................................................................... viii
 List of Figures ................................................................................................................................ ix Abstract .......................................................................................................................................... xi 1. Liming induced changes in arsenic dissolution from mine wastes using phreeqc ......................1
 1.1
 Abstract ................................................................................................................................1 1.2 Introduction ..........................................................................................................................1 1.3
 Literature Review .................................................................................................................3
 1.3.1

Solubility of Arsenic Solid Phases ..............................................................................3
 1.3.2

Adsorption of As by Soils and As Complexation ........................................................3
 1.3.3

Effect of pH on As Sorption ........................................................................................4
 1.4
 Method .................................................................................................................................6
 1.5
 Results ..................................................................................................................................9
 1.6
 Conclusion .........................................................................................................................11 2. A qualitative analysis of bulk conductivity to investigate the process of formation of residual non-aqueous phase liquid in a water-wet system ..........................................................................38
 2.1
 Abstract ..............................................................................................................................38
 2.2
 Introduction ........................................................................................................................38
 2.3
 Literature Review ...............................................................................................................39
 2.3.1

Electrical conductivity ...............................................................................................39
 2.3.2 NAPL Entrapment .....................................................................................................40
 2.4
 Method ...............................................................................................................................42
 2.5
 Results ................................................................................................................................44
 2.6
 Conclusion .........................................................................................................................47 3. Experimental investigation of mechanism of formation of residual non-aqueous phase liquid in a water-wet system ....................................................................................................................52
 3.1
 Abstract ..............................................................................................................................52
 3.2
 Introduction ........................................................................................................................52
 3.3
 Literature Review ...............................................................................................................53
 3.4
 Method ...............................................................................................................................58
 vi 3.5
 Results ................................................................................................................................60
 3.6
 Conclusion .........................................................................................................................62 4. Synthesis .....................................................................................................................................68 Appendix A: Column leachate parameters ....................................................................................71 Appendix B: Examples of PHREEQC input files ..........................................................................78
 Appendix C: Tifton soil series ...................................................................................................... 84
 Appendix D: Particle size analysis ............................................................................................... 89
 Appendix E: Calibration curve ..................................................................................................... 90
 References ......................................................................................................................................92 Biographical Sketch .......................................................................................................................97 vii LIST OF TABLES Table 1-1: Al and Fe equilibrium phases for the mine wastes. ..................................................... 14
 Table 1-2: Al and Fe equilibrium phases for the mine wastes. ..................................................... 15 Table 3-1: Events and effects on the residual oil saturation (Wipfler and van der Zee, 2001)… 64 Table A-1: Column leachate parameters for Opportunity Tailing samples (Kelly, 2005) ........... 71
 Table A-2: Column leachate parameters for Clark Fork Tailing samples (Kelly, 2005) ............. 72
 Table A-3: Column leachate parameters for Red Sand Tailing samples (Kelly, 2005) ............... 73
 Table A-4: Column leachate parameters for Streamside Tailing samples (Kelly, 2005) ............. 74
 Table A-5: Column leachate parameters for Rimini-09 samples (Kelly, 2005) ........................... 75
 Table A-6: Column leachate parameters for Rimini-17 samples (Kelly, 2005) ........................... 76
 Table A-7: Column leachate parameters for Rimini-43 samples (Kelly, 2005) ........................... 77 Table C-1: Location details for soil quarry. ………………………………..……………………84 Table C-2: Primary physical and chemical characterictics data. …… ……………… …………85 viii LIST OF FIGURES Figure 1–1: Anaconda Smelter Superfund Site and portion of Silver Bow Creek/Butte Area Superfund Site. (Kelly, 2005) ....................................................................................................... 16
 Figure 1–2: Silver Bow Creek/Butte Area Superfund Site. (Kelly, 2005) ................................... 16
 Figure 1–3: Portion of Upper Tenmile Creek Mining Area Superfund Site.(Kelly, 2005) .......... 17
 Figure 1–4: Concentration of elements in unlimed and limed Rimini-09 samples and the change in concentration (∆) after liming. .................................................................................................. 19
 Figure 1–5: Concentration of elements in unlimed and limed Rimini-17 samples and the change in concentration (∆) after liming. .................................................................................................. 22
 Figure 1–6: Concentration of elements in unlimed and limed Rimini-43 samples and the change in concentration (∆) after liming. .................................................................................................. 25
 Figure 1–7: Concentration of elements in unlimed and limed Red Sand Tailing samples and the change in concentration (∆) after liming. ..................................................................................... 28
 Figure 1–8: Concentration of elements in unlimed and limed Opportunity Tailing samples and the change in concentration (∆) after liming. ................................................................................ 31
 Figure 1–9: Concentration of elements in unlimed and limed Streamside Tailing samples and the change in concentration (∆) after liming. ..................................................................................... 34
 Figure 1–10: Concentration of elements in unlimed and limed Clark Fork Tailing samples and the change in concentration (∆) after liming. ................................................................................ 37
 Figure 2–1: Wenner array of electrodes used in resistance measurements, two current electrodes (C1 and C2) and two potential electrodes (P1 and P2), a represents the electrode spacing ......... 48
 Figure 2–2: Configuration of spheres and fluids just before the oil rings disconnect. (Wipfler and van der Zee, 2001) ........................................................................................................................ 48
 Figure 2–3: Cartoons depicting NAPL imbibition in the pore spaces. In (a), small pores and pore wedges are filled with NAPL before the larger pore bodies are filled. After these smaller spaces are filled, the NAPL is assumed to be immobile (red). In (b), the pore system is NAPL-filled with the mobile (free) NAPL shown as pink. Water is blue and solid particles are grey. (Lenhard et al. 2004) .................................................................................................................................... 49
 Figure 2–4: Schematic diagram of experiment setup. .................................................................. 49
 Figure 2–5: 1625 Fluke Earth/Ground Tester. .............................................................................. 50
 Figure 2–6: Plot of EC vs θ for first set of experiment . .......................................................... 50
 a eff Figure 2–7: Plot of EC vs θ for second set of experiment . ...................................................... 51
 a eff Figure 2–8: Plot of EC vs θ for third set of experiment . ......................................................... 51
 a eff Figure 3–1: Oil lens on a water film (Film coats the solid surface). (Wipfler and van der Zee, 2001) ............................................................................................................................................. 64
 Figure 3–2: Schematic diagram of experiment setup. .................................................................. 64
 Figure 3–3:Tensiometer from Soil Measurement Systems. .......................................................... 65
 Figure 3–4: Campbell Scientific datalogger CR-800 .................................................................... 65
 Figure 3–5: Plot of h vs S . Comparing measured S to modeled S. ........................................... 66
 o t t t Figure 3–6: Plot of h vs S . Comparing measured S to modeled S. ........................................... 66
 o t t t Figure 3–7: Plot of h vs S . Comparing measured S to modeled S. ........................................... 66
 o t t t Figure 3–8: Plot of h vs S Comparing S based on two assumptions. ...................................... 67
 o w. w ix