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SOURCE APPORTIONMENT AND CHEMICAL CHARACTERIZATION OF TRACE ELEMENTS IN SUSPENDED PARTICULATE MATTER AT KOLHAPUR CITY Thesis Submitted in partial fulfilment of the requirements for the degree of DOCTOR OF PHILOSOPHY by ATUL BALWANT AYARE DEPARTMENT OF CHEMICAL ENGINEERING NATIONAL INSTITUTE OF TECHNOLOGY KARNATAKA, SURATHKAL, MANGALORE 575 025 July, 2014 DECLARATION I, Mr. Atul Balwant Ayare hereby declare that the Research Thesis entitled “Source Apportionment and Chemical Characterization of Trace Elements in Suspended Particulate Matter at Kolhapur City” which is being submitted to the National Institute of Technology Karnataka, Surathkal in partial fulfilment of the requirements for the award of the Degree of Doctor of Philosophy in Chemical Engineering is a bonafide report of the research work carried out by me. The material contained in this Research Thesis has not been submitted to any University or institution for the award of any degree. Signature of the Research Scholar Name : ATUL BALWANT AYARE Register Number : CH07P01 Department : Chemical Engineering Place : NITK, Surathkal Date : CERTIFICATE This is to certify that the Research Thesis entitled “Source Apportionment and Chemical Characterization of Trace Elements in Suspended Particulate Matter at Kolhapur City” submitted by Atul Balwant Ayare (Register No. CH07P01) as the record of the research work carried out by him, is, accepted as the Research Thesis submission in partial fulfilment of the requirements for the award of degree of Doctor of Philosophy. Research Guide (Name and Signature with Date & Seal) Chairman-DRPC (Name & Signature with Date & Seal) ACKNOWLEDGEMENT Though only my name appears on the cover of this dissertation, a great many people have contributed to its production. I owe my gratitude to all those people who have made this dissertation possible and because of whom my Doctoral study experience has been one that I will cherish forever. I take this opportunity to express my profound gratitude and deep regards to my guide Dr. G. Srinikethan for his exemplary guidance, monitoring and constant encouragement throughout the course of this thesis. The blessing, help and guidance given by him time to time shall carry me a long way in the journey of life on which I am about to embark. I offer my sincerest gratitude to him who has supported me throughout my thesis with his patience and knowledge whilst allowing me the room to work in my own way. I attribute the level of my Doctoral degree to his encouragement and effort and without him this thesis, too, would not have been completed or written. One simply could not wish for a better or friendlier supervisor. I have been amazingly fortunate to have him as an Advisor who gave me the freedom to explore on my own and at the same time the guidance to recover when my steps faltered. His patience and support helped me overcome many crisis situations and finish this dissertation. I would like to express my deepest appreciation to Dr. Mrs. Khaparde, Scientist. National Environmental Engineering Research Institute, Nagpur for being external examiner for PhD Viva-Voce Presentation and valuable suggestions. I take this opportunity to thank members of Research Progress Assessment Committee (RPAC) Dr. Vidya Shetty, Head of Department of Chemical Engineering, Dr. M.B. Saidutta, Dr. B. Rajmohan and Dr. Subhash Yaragal of Department of Civil Engineering whose contribution in stimulating suggestions and encouragement helped me to coordinate my project especially in writing this report. I also take this opportunity to express a deep sense of gratitude to the Director of NITK, Deans, Associate Deans, Registrars, Former Heads of Chemical Department Dr. Gopal Mugeraya and Dr. M. B. Saidutta and faculty, technical staff of Chemical Engineering for their cordial support, valuable information and guidance, provision of necessary facilities which helped me in completing this research task through various stages. I am obliged to Dr. D. V. R. Murthy, Professor of Chemical Engineering, Dr. S. Shrihari, Professor of Civil Engineering, Dr. Dwarkish. Associate Professor of Applied Mechanics and other faculty members at Department of Chemical Engineering for the valuable information provided by them in their respective fields. I am grateful for their cooperation during the period of my assignment. In the various laboratories, workshops, and office work, I have been aided for many years by Mr. Sadashiva, Ms. Shashikala and all the staff members of Department of Chemical Engineering who provided something much greater in all the years I've known them: a friendly smile and a hello every time we met. Many Research students and friends at NITK have helped me stay sane through these years. Their support and care helped me overcome setbacks and stay focused on my Doctoral study. I greatly value Dr. Ravishankar, Dr. Madhukar Dabhade, Ms. Aparna A., Ms. Aishwarya, Mr. Keshav Joshi, Ms. Pavitra, Mr. Nitin Patil, Mr. Abhinandan Dhavale for their friendship and I deeply appreciate their belief in me. I am grateful to the Mnagement of Kolhapur Institute of Technology, Kolhapur, Maharshtra, the Principal, Members of Administration and office, faculty, staff of KIT’s College of Engineering, Kolhapur, Maharashtra for their encouragement and co- operation.. The entirety of my thesis has been completed with great help and co-operation by my friend Er. Yogesh Sathe, Assistant Engineer at C-Dac, Pune, Maharshtra. I owe my sincere thanks to him whole heartily. I am especially grateful to my parents, who supported me emotionally and financially. To my Father Late Mr. Balwant Bhausaheb Ayare, thank you for encouraging me in all of my pursuits and inspiring me to follow my dreams. I always knew that you believed in me and wanted the best for me. Thank you for teaching me that my job in life was to learn, to be happy, and to know and understand myself; only then could I know and understand others. Above all, I would like to thank my Mother Smt. Lobha Ayare for her personal support and great patience at all times. I owe you a lot and thank you for your faith in me and allowing me to be as ambitious as I wanted. It was under your watchful eye that I gained so much drive and an ability to tackle challenges head on. It was a great comfort and relief to know that you were willing to provide management of our household activities while I completed my work. My heartfelt thanks to you. My sisters Ms. Swati and Ms. Purva and their families have given me their unequivocal support throughout, as always, for which my mere expression of thanks likewise does not suffice. During this journey, my father in law and mother in law with their sons were so much supportive and co-operative for which they deserve special thanks. Most importantly, I would like to thank my wife Ms. Arati Ayare. Her support, encouragement, quiet patience and unwavering love were undeniably the bedrock upon which the past Eleven years of my life have been built. Her tolerance of my occasional moods is a testament in itself of her unyielding devotion and love. My completion of this project could not have been accomplished without the support of Master Aryan, Elder Son and Master Arin, Younger Son. Thank you for allowing me time away from you to research and write a thesis. You deserve Xbox One! Last but not least, I would like to thank Dr. Anilraj Jagdale, my teacher, colleague and family friend who have supported me throughout entire process, both by keeping me harmonious and helping me putting pieces together. I will be grateful forever for your love. Dedicated to Late Balwant Bhausaheb Ayare My Father and Smt. Lobha Balwant Ayare My Mother ABSTRACT Ambient air pollution in an increasingly urbanized world directly threatens the health of a large fraction of the world’s population. There is a growing recognition that air-borne emissions from major urban and industrial areas influence both air quality and climate change on scales ranging from regional up to continental and global. Deteriorating urban air quality affects the viability of important natural and agricultural ecosystems in regions surrounding highly urbanized areas, and significantly influences regional atmospheric chemistry and global climate change. This challenge is particularly acute in the developing world where the rapid growth of megacities (cities having population equal to or more than 10 million) is producing atmospheric pollution of unprecedented severity and extent. For example, the deterioration of air quality is a problem that is directly experienced by a majority of the 300 million urban Indians, about 30% of India’s population. In developing countries, migration from the countryside to the megacities has brought as a consequence greater emissions into the atmosphere. This is mainly produced by the increase of vehicular traffic; a problem exacerbated by the tendency in these countries to have a stock of old and badly maintained vehicles and badly maintained roads. At the same time, the number of vehicles in circulation has increased as well. These factors have produced far-reaching changes in air quality in urban contexts, especially in the 1990s, when the majority of clean air plans were tightened up. The urban area has expanded with a result that urban population is now closer to Industrial establishments. Airborne particles which result from chemical and allied industries are nothing but heavy metals and aerosols contains reactive, corrosive and carcinogenic chemical molecules. Trace elements are released into the atmosphere by human activities, such as combustion of fossil fuels and wood, high temperature industrial activities and waste incineration. The combustion of fossil fuels constitutes the principal anthropogenic source of Ba, V, Co, Ni, Se, Mo, Sn, Sb, and Hg, and particularly of Cr, Mn, Cu, Zn, and As. High percentages of Ni, Cu, Zn, As, and Cd are emitted from industrial metallurgical processes.

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