ON THE REACTIVITY OF NANOPARTICULATE ELEMENTAL SULFUR: EXPERIMENTATION AND FIELD OBSERVATIONS Fotios Christos Kafantaris Submitted to the faculty of the University Graduate School in partial fulfillment of the requirements for the degree Doctor of Philosophy in the Department of Earth Sciences, Indiana University December 2017 ii Accepted by the Graduate Faculty of Indiana University, in partial fulfillment of the requirements for the degree of Doctor of Philosophy. Doctoral Committee ___________________________ Gregory K. Druschel, PhD, Chair ___________________________ Kevin Mandernack, PhD ___________________________ William P. Gilhooly III, PhD ___________________________ Gabriel Filippelli, PhD ___________________________ Steven E. Lacey, PhD October 2, 2017 ___________________________ Brandy M. Toner, PhD iii © 2017 Fotios Christos Kafantaris iv DEDICATION I would like to dedicate this work to three women. The first one is the Most Holy Theotokos and Ever-Virgin Mary, the most precious individual the human race has and will ever have, the Bridge from earth to Heaven and the Gate to Paradise. Through Her intercessions to the Holy Trinity I am still alive and safe. The second woman is my mother, Eleni, who is the angel-on-earth that protects, nourishes, teaches, provides, inspires and guides me in life. Words would be poor to attempt to describe her and her virtues in an accurate manner. My mother is the main contributor of what I have become so far in life. The third woman is my σύζυγος (spouse) Diana, who has given me life, as well as meaning for life. Diana is the main contributor of what I will hopefully do in life from this point onward, and through her help I will hopefully manage to be with the other two forever. v ACKNOWLEDGEMENTS This work would not have been possible without the spiritual, psychological, financial and academic support of many people. First and foremost, I thank the Holy, Co-substantial, Live-giving and Undivided Trinity for my existence and salvation, and for Her infinite and unconditional Love. I thank my parents Antonios-Pavlos and Eleni for being the reflectance of this unconditional love towards me and my family, and for always believing in me. My dad has always been a great-role model, a perfect example of optimism, motivation and hard work. My mother has been the perfect psychoanalyst and the person who would always make trouble go away with just one smile. Both of them make a perfect match and a superb model for couples and parents. I wish I become like them one day. Along with my parents, my grandfather, Fr.Theodoros, and grandmother, Chrysoula, have always been the continuity of my parents and a source of unconditional love. Without my parents and grandparents nothing would matter. Equal to my family, I thank the Most-Holy Theotokos, St. Nektarios, St. Nikolaos, St. Filothei, St. Anthony, St. Theodore the Warrior, Sts. Kostantine and Helen, St. Artemios, as well as Sts. Paisios, Porfyrios and Iakovos the newly proclaimed, as well as St. Luke of Krimea the Doctor. Glory be to God all of them are always with me wherever I go. I thank my wife Diana for loving me so much above reason. She is the magnet that pulls me forward, the wind under my wings and the harissa in my lahmajoun. Thanks to my angelic kiddos, “Dino” Antoni and “Babyz” Eleni who teach me every day the meaning of life and along with “Mamacusat” help me discover and improve myself constantly. My dear mama-Sue is due special thanks due to her endless love and support, but mostly because of her patience and understanding, especially when things “sound Greek” to her. I love you dearly! I thank my sister Emilia-Anna for “μου 'βαλε τα γυαλιά” as an example of endurance, perseverance and motivation. She is a true descendant of those who said “ἢ τὰν ἢ ἐπὶ τᾶς”. I want to express infinite gratitude to my spiritual father, Fr. Dragan, and his family Vesna, Marija, Kristina, and Petar, as well as my best friends Fr. Marko and Biljana for welcoming me in Indy with open arms and being always there for me. Biljana vi and Kara thank you for your patience at the cantor stand when I messed up the harmony for over 3 years continuously. Bosa and Dragan and the rest of St Nicholas Parish opened their arms to welcome me from the very first moment I entered the church. I thank my sister-in-law Amy, as well as Loren and Evangeline, for being in my life and for being supportive, patient, and having unconditional love for with me and my family. I thank Yanni and Suzanna for being my “grandparents-away-from-home” and being the first welcoming committee along with Fr. George Al-Dehneh, Mike Sifuentes, Roberto Velarde, and John Olgin when I first stepped foot on American soil in Texas. I don’t forget Fr. Georgios, Fr. Stavros, Dn. Dimitrios and all of the St Nicholas parish in London, as well as Fr. Athanasios, Fr. Timotheos, and Fr. Nabil for shadowing me with their prayers constantly. I thank my friends Dimitrios, Dimitrios and Katerina, Christos and Eleni for their true love towards me and my family and for their advice in life. Dr. Akin Akinwande has been a true and brotherly friend to me and my family on many occasions of our lives, and I thank him for that. Athanasios Godelitsas continued being a great support even after I graduated from his research group at the University of Athens. I thank him and his wife, Konstantina, for the late night Skype talks. In addition, I want to thank all past academic advisors since elementary school that contributed to the shaping of my personality and thought process. Some of those include Mr. Lazaros Maniakas, Mr. Kostas Pliasas, Mr. Pantelis, Mrs. Eleutheria, Mr. Rosakis, and many more. Fotios Fouskas is the academic brother that God sent to me so we can help and accompany each other on the track of science and life. Sue Epps was always there for me and my family full of energy and support. Finally, I want to thank my father-in-law Steve Dugger, my family members Niko, Maria, Vasili, Thodori, Panayoti, Roula, Gianni, as well as my academic family Theresa (Dits) Groth, Samapriya Roy, Nicole Bader, Clinton Broach, Shiva (Ladan) Ahrens, Mick Thomas, Beth Welke, Deborah Nichols, Amy Smith, Reina Hiramatsu, Renata Lafler, Igor Ogashawara, Christa Phelps, Melanie Perello, Kudzai Kaseke, James Harris, Nicolas Clercin, and Giorgos Bakoyannis for their constant love and support throughout the graduate school. Last but not least, I am thankful to Fr. Nikon of New Schete (Mount Athos), +Fr. Athanasios Mitilinaios, as well as Fr. Nikolaos Loudovikos, for accompanying me during long days and nights in the lab while I was listening to their lectures and sermons via youtube. vii I want to express my gratitude to Prof. David Borrok, my first PhD advisor while I was still in UTEP, for taking another job in University of Louisiana and supporting my transition to Prof. Greg Druschel’s lab at IUPUI where I finished the current dissertation. Apart from causing for me to dive in the world of sulfur, David unknowingly contributed for me to meet with my wife Diana. This work was possible thanks to the research grants EAR1304352, EAR1261423, and OCE 1261424, given to Greg Druschel by NSF. Also special thanks are due to IUPUI graduate office for a travel fellowship given in 2016. Within the framework of this work I have been graced to collaborate, interact and exchange ideas with a plethora of great scientists of all levels. With the fear of forgetting someone, I wish to thank Eric Boyd from MSU, Kirk Nordstrom, Blaine McCleskey, and Kate Campbell from USGS, as well as Axel Muller who made an expedition to Yellowstone a fun ride in the wilderness. I thank EJ Crane (Pomona College) for his academic advice, friendly discussions and the time he spent with me while he was visiting IUPUI for a year-long sabbatical. Special thanks are due to Philip Schmitt-Kopplin (Helmholtz Zentrum München) for his great hospitality while visiting his research group, in addition to Sabine Dvorski who shared with me her knowledge on sulfur organic chemistry. The most impressive experience was my immersion into the world of synchrotron chemistry at the facilities of Canadian Light Source thanks to Brandy Toner and Yongfeng Hu. My experience at Yongfeng’s beamline was made much more productive due to his help as well as the help of Qunfeng Xiao and Aimee Maclennan. I would like to thank Brandy Toner and Brandi Kamermans for their great hospitality at University of Minnesota, and for their sharing of knowledge on XANES spectroscopy. Special thanks are due to Alexandra Walczak and Jennifer Houghton for the fruitful discussions on sulfur science as well as career development. David Fike has been a collaborator of my advisor’s that I have met almost immediately when I started the doctorate program. David is a hospitable, generous, kind and inspiring person and I thank him for being in my academic life. I also feel very grateful for having met and worked with Don Nuzzio. Don is an inspiring person and knows how to calm you down when electrodes don’t work. I want to thank Martin Kurek, John Shukle and Chase Howard for their viii tremendous support in the lab and for their encouragement over the last months of my grad school. I want to thank Kevin Mandernack for the long academic and philosophical discussions and for the constant support. Special thanks to Bill Gilhooly, and Gabe Filippelli for being supportive and resourceful along the way of my career in IUPUI.