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Geochemistry of Gas Manifestations in Greece

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Geochemistry of Gas Manifestations in Greece Università degli Studi di Palermo (Palermo, Italy) Dipartimento di Scienze della Terra e del Mare (DISTEM) National and Kapodistrian University of Athens (Athens, Greece) Department of Geology and Geoenvironment Istituto Nazionale di Geofisica e Vulcanologia (sez. Palermo, Italy) Co-supervision PhD in Geochemistry DOTTORATO DI RICERCA IN SCIENZE DELLA TERRA – GEOCHIMICA XXX° CICLO (GEO/08) DOCTORATE OF PHILOSOPHY IN APPLIED AND ENVIRONMENTAL GEOLOGY Geochemistry of Gas Manifestations in Greece PhD thesis by: Kyriaki Daskalopoulou IL COORDINATORE Aiuppa Alessandro SUPERVISORS Parello Francesco Kyriakopoulos Konstantinos CO-SUPERVISORS D’Alessandro Walter CICLO XXX January 2015 – December 2017 Università degli Studi di Palermo (Palermo, Italy) Dipartimento di Scienze della Terra e del Mare (DISTEM) National and Kapodistrian University of Athens (Athens, Greece) Department of Geology and Geoenvironment Istituto Nazionale di Geofisica e Vulcanologia (sez. Palermo, Italy) Co-supervision PhD in Geochemistry DOTTORATO DI RICERCA IN SCIENZE DELLA TERRA – GEOCHIMICA XXX° CICLO (GEO/08) DOCTORATE OF PHILOSOPHY IN APPLIED AND ENVIRONMENTAL GEOLOGY Geochemistry of Gas Manifestations in Greece PhD thesis by: Kyriaki Daskalopoulou IL COORDINATORE Aiuppa Alessandro SUPERVISORS Parello Francesco Kyriakopoulos Konstantinos CO-SUPERVISORS D’Alessandro Walter CICLO XXX January 2015 – December 2017 Στους γονείς μου Κώστα και Έφη, που με δίδαξαν να μάχομαι και να μην τα παρατάω… Στον Νίκο, τον «μικρό πρίγκηπα» που με έμαθε να ονειρεύομαι και να πετάω…. Acknowledgments During the three years of my thesis, many people contributed to this achievement, each one with his way. There is no doubt that my supervisors, Prof. Francesco Parello and Prof. Konstantinos Kyriakopoulos, stood by me all along this research. Always available for any discussion, scientific or not, each of their advice was always illuminating. It is impossible to count the hours we worked together. For these reasons I would like to greatly thank them. Nevertheless, I was lucky enough to have Dr. Walter D’Alessandro as a co-supervisor. Our collaboration counts more than four years, since the time when I was a master student in the Department of Geology and Geoenvironment at the National and Kapodistrian University of Athens. For all these years Dr. Walter D’Alessandro has been a mentor and a friend and I am really grateful to him for his continuous presence and support. Since the beginning of my PhD course, I had the pleasure to collaborate with Dr. Sergio Calabrese, a brilliant researcher of Università degli Studi di Palermo, who provided me with the opportunity to join a multidisciplinary team, and made me “discover” and “travel” in the magic world of Geochemistry and Volcanology. Also, I would like to thank Prof. Franco Tassi for the fruitful discussions regarding the evolution of this project and his helpful advices during these years. My collegue, Manfredi Longo, who helped me with the expansion of the database. Furthermore, I kindly acknowledge Francesco Capecchiacci (GC laboratory, UniFi), Mauro Martelli and Francesco Salerno (GC laboratory INGV-Pa), Ygor Oliveri and Aldo Sollami (MS laboratory INGV-Pa), Andrea Rizzo and Mariano Tantillo (Noble Gas laboratory INGV-Pa) for their kind and valuable support in the analyses. Among them, I am indebted with Dr. Markos Xenakis and Dr. Konstantinos Athanasoulis of the IGME for their precious information about the location of many interesting sites all around the Hellenic territory. I am also grateful for the insightful comments of Andri Stefansson and an anonymous referee and of the editor Hailiang Dong that helped me significantly improve the part of hydrocarbons. I am also indebted to David Hilton, who managed as editor the first round of review of the same manuscript. I was deeply touched by the notice of his death. Also, I kindly acknowledge Prof. Orlando Vaselli and Prof. Carlo Cardellini for their suggestions in the final revision of my thesis. Nevertheless, none of these would have happened without the moral and psychological support of my parents Kostas and Efi Daskalopoulos, who were always there to help me stand on my feet and go forward. Although he is not longer with us, I would like to thank my brother Nikos iv Daskalopoulos, who taught me how to fly and I am sure that he would have been very proud for his little sister. Also, I am grateful to my friends Despoina Zoura, Silvia Milazzo, Luciana Randazzo and Stefano Dell’Aria who showed great patience and gave priceless moral and psychological support during these three years despite my paranoias and stress. Last but not least, the Ministero dell'Istruzione, dell'Università e della Ricerca (MIUR) of Italy is greatly acknowledged for providing me the economic support through the 3-year scholarship, which was essential for accomplishing this task, and of course the Università degli Studi di Palermo and the Istituto Nazionale di Geofisica e Vulcanologia- Palermo are especially thanked for giving me the opportunity to carry out this thesis. v INDEX Acknowledgments ................................................................................................................................... iv ABSTRACT ............................................................................................................................................ 1 RIASSUNTO .......................................................................................................................................... 3 ΠΕΡΙΛΗΨΗ ............................................................................................................................................ 5 Introduction ............................................................................................................................................. 7 1. Study Area ..................................................................................................................................... 10 1.1. Geodynamic and Geotectonic setting ...................................................................................... 10 1.2. Geological regime .................................................................................................................. 12 1.3. Geothermal fields ................................................................................................................... 14 1.4. Heat flow and Crustal Thickness using the new Moho model, an overview ............................. 18 2. Materials and Methods ................................................................................................................... 19 2.1. Sampling methods .................................................................................................................. 19 2.1.1. Free gases………………………………………………………………………………….19 2.1.2. Dissolved gasses…………………………………………………………………………..20 2.2. Analytic methods in the laboratory ......................................................................................... 21 3. Results ........................................................................................................................................... 24 3.1. Chemical composition of the gases ......................................................................................... 24 3.2. Isotope composition of the gases ............................................................................................ 28 4. Discussion ..................................................................................................................................... 30 4.1. Gas Components .................................................................................................................... 30 4.2. Origin and sources of He and CO2 in the gas manifestations of Greece ................................... 32 4.3. Helium isotope values and CO2 concentrations related to Geodynamics and Volcanism .......... 49 4.4. Light Hydrocarbons ............................................................................................................... 56 4.4.1. An overview in the classification of hydrocarbons………………………………………..56 4.4.2. Origin of hydrocarbon compounds in Greece……………………………………………..59 4.4.3. Secondary post-genetic processes………………………………………………………...64 4.5. Environmental Hazards .......................................................................................................... 67 Conclusions ........................................................................................................................................... 70 References............................................................................................................................................. 75 Appendix .............................................................................................................................................. 98 vi FIGURE INDEX Figure 1: Map of the major tectonic structures and the current horizontal stress field main axes. Fault lines derive from the CSSs upper edge of GreDaSS (2014). .............................................. 11 Figure 2: Structural zones of the Hellenides after Mountrakis (1986)......................................... 13 Figure 3: Map of geotectonic zones and thermal springs (Athanasoulis et al., 2009) .................. 15 Figure 4: a) Heat flow map of Greece by Fytikas and Kolios (1979). The heat flow values are presented in mWm-2; b) The new Moho depth model (km) from deep seismic imaging data as proposed by Grigoriadis et al., 2016. ........................................................................................
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