UNIVERSITY OF CYPRUS DEPARTMENT OF CIVIL AND ENVIRONMENTAL ENGINEERING Advanced systems for the enhancement of the environmental performance of wineries - wastewater purification combining biological, advanced chemical and reverse osmosis treatmentIoannou Doctoral Dissertation Lida Ioannou Lida November 2013 UNIVERSITY OF CYPRUS DEPARTMENT OF CIVIL AND ENVIRONMENTAL ENGINEERING Advanced systems for the enhancement of the environmental performance of wineries - wastewater purification combining biological, advanced chemical and reverse osmosis treatment By IoannouLIDA IOANNOU Chemical Engineer, Aristotle University of Thessaloniki, Greece MSc. Environmental Engineering, University of Cyprus, Cyprus Submitted to the Department of Civil and Environmental Engineering of the University of LidaCyprus in partial fulfillment of the requirements of the degree of DOCTOR OF PHILOSOPHY Nicosia, November 2013 Copyright © Lida Ioannou, 2013 All Rights Reserved Ioannou Lida UNIVERSITY OF CYPRUS DEPARTMENT OF CIVIL AND ENVIRONMENTAL ENGINEERING APPROVAL PAGE DOCTOR OF PHILOSOPHY DISSERTATION This is to certify that this dissertation was prepared By Lida Ioannou Titled Advanced systems for the enhancement of the environmental performance of wineries - wastewater purification combining biological, advanced chemical and reverse osmosis treatment complies with the University regulations and meets the standards of the University for originality and quality. Ioannou This dissertation was successfully presented and defended to the examining committee on Monday 11th of November 2013. Academic/ResearchLida Advisor Despo Fatta-Kassinos, Nireas - International Water Research Center, Director Examination Committee Michael Petrou, Professor (Chairman of the Committee) Symeon Christodoulou, Associate Professor Evan Diamadopoulos, Professor Constantina Kapnisi-Christodoulou, Assistant Professor Ph.D. examination committee Academic/Research Advisor Dr. Despo Fatta-Kassinos Nireas - International Water Research Center, Director Department of Civil and Environmental Engineering University of Cyprus Members of the Committee Dr. Michael Petrou Ioannou Professor Dr. Evan Diamadopoulos Department of Civil and Professor Environmental Engineering Department of Environmental University of Cyprus Engineering (Chairman of the Committee) Technical University of Crete Lida Dr. Symeon Christodoulou Associate Professor Dr. Constantina Kapnisi-Christodoulou Department of Civil and Assistant Professor Environmental Engineering Department of Chemistry University of Cyprus University of Cyprus IoannouDedicated to my family Lida ACKNOWLEDGMENTS ACKNOWLEDGMENTS One of the joys of completion is to look over the journey past and remember all the friends and family who have helped and supported me along this long but fulfilling road. I would like to thank first of all and from the bottom of my heart, my supervisor Dr. Despo Fatta-Kassinos, Director of Nireas - International Water Research Center who is not only my mentor but a dear friend. I would like to thank her for the support and confidence in my ability to fulfill this Ph.D thesis, as well as for the assignment of this so interesting topic, her scientific guidance, help and unlimited interest during the implementation of my research work. I appreciate her contribution of time, ideas and funding to make my Ph.D experience productive and stimulating. The joy and enthusiasm she has for her research was contagious and motivational for me, even during the tough times of the Ph.D pursuit. I would also like to warmly thank the other members of my examination committee, Professor Dr. Michael Petrou, Associate Professor Dr. Symeon Christodoulou, Assistant Professor Dr. Constantina KapnisiIoannou-Christodoulou, and Professor Dr. Evan Diamadopoulos for the honor to participate in the committee of my Ph.D thesis, and for their support, guidance and helpful suggestions. I am also very grateful to visiting Professor and senior scientist of Gaia- Laboratory of Environmental Engineering and Nireas - IWRC, Dr. Costas Michael for his scientific advice and knowledge,Lida his encouragement, the many insightful discussions and suggestions, and his humor during the difficult times. I would also like to give a heartfelt, special thanks to Professor Dr. Evan Diamadopoulos and Assistant Professor Dr. Nikos Xekoukoulotakis who offered me the opportunity to work in their laboratories and helped me with the reverse osmosis experiments and the HPLC analysis. Many thanks to the staff and students at the Laboratories of “Environmental Technology and Management” and “Environmental Organic Chemistry - Micropollution” of the Department of Environmental i ACKNOWLEDGMENTS Engineering, at the Technical University of Crete (TUC); especially, Katerina Drosou, Nikos Vakondios, Dr. Theodora Velegraki, Dr. Constantina Tyrovola and Elisavet Koukouraki. Thank you for welcoming me as a friend and helping me to develop various ideas during the work implementation. Many thanks to Assistant Professor Dr. Constantina Kapnisi-Christodoulou who offered me the opportunity to work in her laboratory in the Department of Chemistry, of the University of Cyprus; and to Christiana Georgiou for helping me with the HPLC analysis. I would also like to thank the personnel of the S.K. Euromarket Ltd, for the construction of the two winery wastewater treatment plants (SBR and MBR), as well as the two solar pilot plants. Special thanks to Stathis Kyriakou (owner and director of the company) and Georgia Konstantinidou (Chemical Engineer) for their help and support. I wish to express my appreciation to the personnel of the “Tsiakkas”, “SODAP” and “Stylianoudakis” wineries for the permission of collecting wastewater samples, as well as the State General Laboratory of Cyprus for the permission of using the TOC analyzer. Many thanks to Costas TsiakkasIoannou, manager of “Tsiakkas” winery for his help and the generosity he showed to me. I gratefully acknowledge the funding sources that made this Ph.D work possible. This research was co-funded by the LIFE financial instrument of the European Commission throughLida grant LIFE08/ENV/ 000455, and part of the work has been supported by the activities of the International Research Center “NIREAS” (Strategic Infrastructure Project ΝΕΑ ΥΠΟΔΟΜΗ/ΣΤΡΑΤΗ II/0308/09), which is co-funded by the Republic of Cyprus and the European Regional Development Fund. I would like to thank both organizations for their generous financial support towards the laboratories I worked in. I would like to thank all the present and past members of GAIA-Laboratory of Environmental Engineering and NIREAS-International Water Research Center, for their help and support, as well as for our excellent collaboration. My warmest thanks ii ACKNOWLEDGMENTS to Dr. Evroula Hapeshi, Dr. Irene Michael, Dr. Marlen Ines Vasquez, Constantinos Yiannapas, Toumazis Toumazi, Popi Karaolia, Maria Tarapoulouzi and Raphaela Andreou for their support and for providing a pleasant and productive working atmosphere. Each person listed played a special role in my time here. I also thank my friends for their support and valuable friendship. ‘Thank you for your encouragement, support and most of all your humor.’ Of course the acknowledgments couldn’t be complete without giving thanks to my parents and my sister Elpida. My hard-working parents have sacrificed their lives for my sister and myself and provided unconditional love and care. Especially my mom has instilled many admirable qualities in me and given me a solid foundation to build my upon life. They have taught me to be a hard worker and a self-respect person, persistent and independent. My sister is a great role model of strength and character, and I truly thank her for all the advice’ and support provided to me. I know I always have my family to count on when times are rough. Last but certainly not least, I would like to express my gratitude to my husband, Panayiotis Ttofa. His love, patience, support and unwavering belief in me, have enabled me to complete this long dissertationIoannou journey. He is my biggest fan and supporter. He was taking care of whatever needed tending without complaining during the implementation of my Ph.D thesis, so as I could focus on its completion. I could not have completed this journey without Panayiotis by my side. ‘There are no words that can express my appreciation for all you’ve done and been for me. Thank you with all my Lidaheart and soul.’ Lida Ioannou University of Cyprus November, 2013 iii ABSTRACT ABSTRACT The presence of high organic and inorganic compounds, and the spatio-temporal dynamics of winery wastewater among and within wineries, makes the treatment of winery wastewater challenging. The various wine processing systems applied at each winery, generate wastewater with specific properties, and therefore, establishing a general agreement on the most suitable cost-effective technology for the treatment of this wastewater stream does not seem feasible. Several winery wastewater treatment technologies are available, but the development of alternative ones is essential, in order to increase their efficiency and decrease the investment and operational costs. Five underlying objectives were set to fulfill the overall target of this dissertation. The first was to investigate and identify the environmental impacts related to the wine production process, using Cyprus wineries as a case study, and the various actions that could be implemented by wineries, in order to minimize or eliminate these impacts. The