Biomarker Geochemistry of Core Sediments in the Mangrove Ecosystems along Northern Kerala Coast Thesis submitted to Cochin University of Science and Technology in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Marine Chemistry Under the Faculty of Marine Sciences By Manju M.N Reg. No. 3691 Department of Chemical Oceanography School of Marine Sciences Cochin University of Science and Technology Kochi – 682016 April 2015 Biomarker Geochemistry of Core Sediments in the Mangrove Ecosystems along Northern Kerala Coast Ph.D. Thesis under the Faculty of Marine Sciences Author: Manju M.N Research Scholar Department of Chemical Oceanography School of Marine Sciences Cochin University of Science and Technology Kochi - 682016 Email: [email protected] Supervising Guide: Dr. N. Chandramohanakumar Professor Department of Chemical Oceanography School of Marine Sciences Cochin University of Science and Technology Kochi - 682016 Email: [email protected] April, 2015 COCHIN UNIVERSITY OF SCIENCE AND TECHNOLOGY DEPARTMENT OF CHEMICAL OCEANOGRAPHY Dr. N. Chandramohanakumar Professor [email protected] This is to certify that the thesis entitled “Biomarker Geochemistry of Core Sediments in the Mangrove Ecosystems along Northern Kerala Coast” is an authentic record of the research work carried out by Ms. Manju M.N, under my supervision and guidance at the Department of Chemical Oceanography, School of Marine Sciences, Cochin University of Science and Technology, Kochi-682016, in partial fulfilment of the requirements for Ph.D degree of Cochin University of Science and Technology and no part of this has been presented before for any degree in any University. I further certify that all the relevant corrections and modifications suggested by the audience during the Pre-synopsis Seminar and recommended by the Doctoral Committee of Ms. Manju M. N has been incorporated in the thesis. Dr. N. Chandramohanakumar (Supervising Guide) Kochi - 682016 April, 2015 I hereby declare that the thesis entitled “Biomarker Geochemistry of Core Sediments in the Mangrove Ecosystems along Northern Kerala Coast” is an authentic record of the research work carried out by me under the guidance and supervision of Dr. N. Chandramohanakumar, Professor, Department of Chemical Oceanography, School of Marine Sciences, Cochin University of Science and Technology, and no part of this has previously formed the basis of the award of any degree, diploma, associateship, fellowship or any other similar title or recognition from any University/Institution. Kochi-16 Manju M.N April, 2015 I would like to take this opportunity to thank all the persons who helped me to commence and complete my research work. I would like to acknowledge them for their efforts, assistance and collaboration which have worked towards the success of this study. I am deeply grateful to my supervising guide, Dr. N. Chandramohanakumar, for patiently taking me through this difficult task of research. I express my deep and sincere gratitude to my guide for conceptualisation and implementation of this research topic, in addition to his peerless guidance and motivation throughout my research. I am thankful to Dr. Sujatha C.H., Head, Department of Chemical Oceanography for her valuable suggestions and encouragement during the tenure of my work. I do not have words to acknowledge Dr. Jacob Chacko and Dr. S. Muraleedharan Nair, for their help and encouragement throughout the course of my research. I am grateful to Dr. Mohan Kumar, K., Director, School of Marine Sciences and Dr. Sajan, K., Dean, Faculty of Marine Science, for providing facilities for the research work. I owe special thanks to my classmate Dr. Ratheesh Kumar C.S, for his unstinted support all through the course of this research work. I am grateful to Mrs. Resmi P, for her help and motivation throughout the study. I am thankful to Dr. Gireeshkumar T.R, Mrs. Nebula Murukesh, Dr. Martin G.D, Ms. Saritha S, Ms. Movitha Mohandas, Dr. Manju Mary Joseph and Dr. Renjith K.R, for their assistance in the entire phase of my research work. I would like to thank Mr. Salas P.M, Mr. Sanil Kumar, Dr. Prasob Peter, Dr. Deepulal P.M, Mrs. Ragi A.S, Mrs. Leena P.P, Ms. Ramzi A, Dr. Shaiju P, Mrs. Bindu K.R, Mr. Rahul R, Mr. Udayakrishnan P.B, Mr. Manu Mohan, Mr. Shameem and Mr. Akhil P Soman, for their inspired advice, continuous encouragement and support. I extend my special gratitude towards Dr. Aninda Sarkar, Professor, Department of Geology and Geophysics, IIT Kharagpur, for stable carbon isotope analysis. I sincerely acknowledge the help rendered by SAIF Lab, STIC, Cochin University of Science and Technology for instrumental analysis. I thank staff of Sophisticated Analytical Instrumentation Facility, CUSAT, for CHNS analysis. I take this opportunity to thank the non- teaching staff of Department of Chemical Oceanography and Cochin University of Science and Technology for helping the administrative work of my thesis. I would like to thank my father, mother, elder sister and brother- in- law for their support, patience, and for their continued inspiration over the years. I am thankful to Dr.Venugopal R, for his valuable advice and encouragement. I would like to thank almighty (God), to bless me by giving the potential to complete this enormous task. MANJU M.N Preface Mangroves are diverse group of trees, palms, shrubs, and ferns that share a common ability to live in waterlogged saline soils exposed to regular flooding, and are highly specialised plants which have developed unusual adaptations to the unique environmental conditions. They are sites of accumulation and preservation of both allochthonous and autochthonous organic matter owing to their strategic loction at the interface between land and sea and prevailing reducing environment. They are among the most productive ecosystems and are efficient carbon sinks with most of the carbon stored in sediments.Mangrove ecosystems play a significant role in global carbon cycle and hence the knowledge on the processes controlling the delivery of organic matter to coastal sediments, and how these signatures are preserved in the sediment is a prerequisite for the understanding of biogeochemical cycles. The evaluation of nature and sources of organic matter can be accomplished by the determination of biochemical constituents like carbohydrates, proteins and lipids. When characterised at molecular level, lipids provide valuable information about the sources of organic matter, even though they account only small fraction of organic matter. They are useful for the paleo-environmental reconstruction because of their low reactivity, high preservation potential and high source specificity relative to other organic class of compounds. The application of recent analytical techniques has produced a wealth of useful information but has also indicated the gaps in our knowledge on cycling of organic matter in the coastal ecosystems. The quantity and quality of organic matter preserved in sediments vary depending up on the nature of material delivered to the sediment and on the depositional environment. The input from both autochthonous and allochthonous sources sharpens the complexity of biogeochemistry of mangrove ecosystem and hence bulk sedimentary parameters are not completely successful in evaluating the sources of organic matter in mangrove sediments. An effective tool for the source characterisation of organic matter in coastal ecosystems is biomarker approach. Biomarkers are chemical "signatures" present in environmental samples whose structural information can be linked to its biological precursor. The usefulness of molecular biomarkers depends on high taxonomic specificity, potential for preservation, recalcitrant against geochemical changes, easily analysable in environmental samples and should have a limited number of well-defined sources. The thesis entitled “Biomarker Geochemistry of Core Sediments in the Mangrove ecosystems along Northern Kerala Coast” is an attempt to characterise the sources of organic matter in the core sediments of mangrove forests providing special emphasis on lipid biomarkers such as n-alkanes and fatty acids. Core sediment samples were collected from five mangrove ecosystems along Northern Kerala coast, Southwest India. In this study, a combination of bulk geochemical parameters and different groups of molecular biomarkers has been used to define organic matter sources and thereby identifying various biogeochemical processes acting in the study region. Core sediments were used in this study because they can provide long term and continuous past historical records and act as a useful tool for the effective reconstruction of past environmental conditions. The thesis is divided into six chapters. Chapter 1 is Introduction and it contains general aspects of mangrove ecosystems, the aim and scope of the study. Chapter 2 is Materials and methods. This chapter deals with the nature and general geographical features of the study area. It also contains the details of the sampling and analytical methodology. Chapter 3 is Geochemistry of heavy metals, which includes the down core variations of the general sedimentary parameters,
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