Chemical and Physical Dynamics of Marine Pockmarks with Insights Into the Organic Carbon Cycling on the Malin Shelf and in the Dunmanus Bay, Ireland

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Chemical and Physical Dynamics of Marine Pockmarks with Insights Into the Organic Carbon Cycling on the Malin Shelf and in the Dunmanus Bay, Ireland CHEMICAL AND PHYSICAL DYNAMICS OF MARINE POCKMARKS WITH INSIGHTS INTO THE ORGANIC CARBON CYCLING ON THE MALIN SHELF AND IN THE DUNMANUS BAY, IRELAND BY Michal Szpak, M.Sc. Thesis submitted for the Degree of Doctor of Philosophy Supervisor: Dr Brian Kelleher Dublin City University School of Chemical Sciences March, 2012 Declaration I hereby certify that this material, which I now submit for assessment on the programme of study leading to the award of Doctor of Philosophy is entirely my own work, that I have exercised reasonable care to ensure that the work is original, and does not to the best of my knowledge breach any law of copyright, and has not been taken from the work of others save and to the extent that such work has been cited and acknowledged within the text of my work. Signed: ____________ (Candidate) ID No.: ___________ Date: _______ Abstract Pockmarks are specific type of marine geological setting resembling craters or pits. They are considered surface expression of fluid flow in the marine subsurface. Pockmarks are widespread in the aquatic environment but the understanding of their formation mechanisms, relationship with marine macro- and micro-biota and their geochemistry remains limited. Despite numerous findings of these features in Irish waters they received little attention and remain poorly studied. In this work extensive geophysical data sets collected by the Irish National Seabed Survey and its successor the INFOMAR project as well in situ sediment samples were utilized to provide baseline information on the nature of some of these features, the processes they are fuelled by and their geochemical characteristics. Pockmarks from open shelf (Malin Shelf) and bay, fjord like environment (Dunmanus Bay) are compared and theories of their formation are formulated. Sediment from these features was extensively studied utilizing advanced geotechnical and geochemical tools to describe and quantify processes taking place in the subsurface. Organic matter was characterized on a molecular level by combined biomarker and advanced Nuclear Magnetic Resonance approach. I Acknowledgements The research of which fruits are presented in this thesis was a wonderful journey, full of exploration of scientific ideas, acquiring knowledge and learning about inner strengths and weaknesses. This journey would not be possible if not the support and dedication of many people. I would like give my thanks to all of them and express gratitude for their support in all of the good and bad moments that I have encountered while working on this project. I would like to dedicate this thesis to my wife Justyna. Your unflinching support, love and patience were the biggest source of strength and motivation I needed to complete this work. To my parents Janusz and Teresa as well as my brother Łukasz, I thank You for the instilled values that led me to pursue a degree in science: curiosity of the world, ambition and perseverance. Special thanks go to my mentor Brian Kelleher for giving me continuous support, advice, for his great resourcefulness and encouragement and for being a good friend. I thank my collaborators and partners in the Geological Survey of Ireland, Xavier Monteys and Koen Verbruggen for sharing their time and knowledge and for making my off shore experience possible. I also would like to thank the crew and the captains of the RV Celtic Explorer and RV Celtic Voyager as well as all staff from Irish Marine Institute for their expertise and help given during the preparation and execution of all research cruises I had the privilege to participate in. Special thanks to Andrew Simpson, his research group and technical staff for the invaluable help in acquiring NMR spectra and for their advice and insight during their interpretation. I also would like to thank to my colleagues Kris Hart, Shane O’Reilly, Sean Jordan, Vasileios Kouloumpos, Leon Barron, Adrian Spence, Margaret McCaul, Brian Murphy, Brian Moran, Carla Meledandri for all the hours of productive and purely fun coffee breaks we have spent together breaking the often so tedious laboratory routine. Finally I would like to give my thanks to all academic and technical staff of the School of Chemical Sciences, Dublin City University for Your support and advice during this project. II Declaration Bathymetry, backscatter and sub bottom data was collected in 2003, 2006 and 2007 as part of the INSS (Irish National Seabed Survey) program and its successor, the INFOMAR (Integrated Mapping for the Sustainable Development of Ireland's Marine Resources) program (Dorschel et al., 2010). The data was accessed through collaboration with the Geological Survey of Ireland (GSI) and Irish Marine Institute (MI) and in accordance with the open and free access policy announced by The Minister for Communications, Marine and Natural Resources, Mr. Noel Dempsey T.D. in 2007. Towed electromagnetic (EM) data were acquired during a geo-hazard and hydrocarbon reconnaissance survey of the Malin Shelf in 2009 (GSI/PIP – IS05/16 project, Monteys et al., 2009 and Gracia et al., 2009). The data was accessed through collaboration with the Dr Xavier Monteys, Dr Koen Verbruggen (GSI), Dr Xavier Garcia (Dublin Institute for Advanced Studies, Ireland) and Dr Rob Evans (Woods Hole Oceanographic Institution, USA). The result of this collaboration was published as Szpak et al., 2011. The author acknowledges that ownership and credit for the acquisition and processing of the above mentioned data is that of the above mentioned institutions and individuals. The authors own work involved manipulation and interpretation of the data in a novel way not pursued by any of the data owners. The NMR experiments were performed by Prof Andre Simpson (Environmental NMR Center, University of Toronto, Canada). All sample preparation and interpretation of the results was conducted by the author. Foraminifer counting was performed by Dr Soledad Garcia-Gil (Dpto Geociencias Marinas, University of Vigo, Spain). Sample pre-concentration and results interpretation was conducted by the author. Pore water sulphate and chloride analysis of the Dunmanus Bay core was performed by Dr Carlos Rocha (Trinity College Dublin, Ireland). Benthic survey along with data processing and preliminary interpretation was conducted as contract analysis by AQUAFAC International Services Ltd., Ireland during research cruise CE09_023 organized and led by the author. III Table of Contents ABSTRACT ............................................................................................................................... I ACKNOWLEDGEMENTS ...................................................................................................... II DECLARATION ...................................................................................................................... III TABLE OF CONTENTS ......................................................................................................... IV CHAPTER 1 - INTRODUCTION ............................................................................................. 1 1.1 POCKMARKS AS SEABED STRUCTURES .................................................................... 1 1.1.1 WHAT ARE POCKMARKS? .............................................................................................................. 1 1.1.2 HISTORICAL BACKGROUND ........................................................................................................... 2 1.1.3 FORMATION OF POCKMARKS ........................................................................................................ 3 1.1.4 DETECTION OF POCKMARKS, SHALLOW GAS AND OTHER FLUIDS IN THE WATER COLUMN AND THE SUB SURFACE ........................................................................................................................................ 6 1.1.5 THE DISTRIBUTION OF POCKMARKS AROUND THE WORLD .......................................................... 10 1.1.6 THE DISTRIBUTION OF POCKMARKS AROUND GREAT BRITAIN AND IRELAND ............................. 11 1.1.7 IMPORTANCE OF POCKMARKS AND POCKMARK RELATED FLUID FLOW OCCURRENCES ............... 14 1.1.7.1 CONTRIBUTION TO CARBON CYCLE ..................................................................................... 14 1.1.7.2 POCKMARKS AND GAS AND OIL EXPLORATION ................................................................... 19 1.1.7.3 POCKMARKS AND GAS HYDRATES ...................................................................................... 22 1.1.8 DO POCKMARKS CONTRIBUTE TO THE FOOD WEB? ..................................................................... 22 1.1.9 POTENTIAL AND DANGERS ASSOCIATED WITH POCKMARKS ....................................................... 25 1.2 CARBON CYCLING ......................................................................................................... 27 1.2.1 THE GLOBAL CARBON CYCLE ..................................................................................................... 27 1.2.2 COASTAL CARBON CYCLE .......................................................................................................... 31 1.2.3 THE ORGANIC CARBON CYCLE .................................................................................................... 34 1.3. ASPECTS OF METHODOLOGY .................................................................................... 37 1.3.1 PHYSICAL PROPERTIES OF SEDIMENTS ........................................................................................ 37 1.3.1.1 PARTICLE SIZE DISTRIBUTION ............................................................................................
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