PHYSICAL AND GEOCHEMICAL CHARACTERISATION OF CANAL SEDIMENTS IN THE BLACK COUNTRY, WEST MIDLANDS. A thesis presented for the degree of Doctor of Philosophy by Danen Appasamy B.Sc.(Hons.) University of Wolverhampton Research Centre in Applied Sciences University of Wolverhampton PHYSICAL AND GEOCHEMICAL CHARACTERISATION OF CANAL SEDIMENTS IN THE BLACK COUNTRY, WEST MIDLANDS. A thesis submitted in fulfilment of the requirements of the University of Wolverhampton for the award of the degree of Doctor of Philosophy (Ph.D.) December 2011 This work or any part thereof has not previously been submitted in any form to the University or to any other body whether for the purpose of assessment, publication or for any other purpose. Save for any express acknowledgements, references and/or bibliographies cited in the work, I confirm that the intellectual content of the work is the result of my own efforts and no other person. The right of Danen Appasamy to be identified as author of this work is asserted in accordance with ss. 77 and 78 of Copyright, Designs and Patents Act 1988. At this date copyright is owned by the author. Signature: D.Appasamy Date: 1st December 2011 ii ABSTRACT otentially harmful elements (PHEs) have been researched in a wide variety of disciplines, including pedology, chemistry, pollution science and medicine. Within the Pscientific community, emphasis has usually been placed on the toxic elements, such as cadmium, chromium, lead and arsenic, but rarely has there been consideration of interactions between PHEs, the sediment matrix and processes occurring in the sediments. Dredging of canals is needed for navigability purposes and consequently testing of dredged sediments (to assess whether sediments are hazardous) and landfilling can be costly for British Waterways facing constantly changing regulations and reduction in government grants. PHE mobility and availability in canal sediments can be affected by oxygen availability, pH and Redox. Remediation is thus becoming a priority for British Waterways to limit their operational costs. Zeolites, a type of remediation tool, have been widely studied in the past 30 years due to their attractive properties, such as molecular-sieving, high cation exchange capacities and their affinity for PHEs. The pilot study to investigate the efficiency of the clinoptilolite showed that there was a concentration difference between PHEs adsorbed by the clinoptilolite and the PHE concentration lost from the sediments from three sites in the West Midlands. Thorough characterisation of the sediments was needed to understand the speciation of the PHEs and the secondary processes occurring in the sediments. The different components of the sediments were analysed using various analytical methods, such as X-Ray Fluorescence spectroscopy (XRF), particle size and X-ray Diffraction (XRD) for the solid-inorganic phase, Ion Chromatography (IC) and Inductively Coupled Plasma-Optical Emissions Spectroscopy (ICP- OES) for the liquid phase (pore water), Gas Chromatography-Mass Spectrometry (GC-MS) and organic loss on ignition for the organic phase, pH and Redox for the electrochemistry of the sediments and Scanning Electron Microscope with Energy Dispersive X-Ray analysis (SEM-EDX) for microscopy and imaging. The British Geological Survey (BGS) sequential extraction method was used to investigate the different phases in the sediments. pH remained near neutral for all three sites and Redox remained anoxic. Organic contents for all three sites were around 30% and contained most of the polycyclic aromatic hydrocarbons considered hazardous. Pore water showed only high concentrations of sulphates but low concentrations of PHEs, suggesting PHEs were not mobile. Sequential extraction confirmed the other results showing that PHEs were mainly associated with stable phases, such as iron and manganese oxides or sulphides. The results have been taken into consideration to design a new remediation strategy to maximise efficiency of the zeolite. iii ACKNOWLEDGEMENTS have spent the last six years studying environmental management and developed an interest in sediment characterisation and remediation during the final year of my I undergraduate studies. During these 6 years, I have met and made numerous friends who have helped me in one way or another during this Ph.D research activity. Firstly, I am most grateful to my doctoral team, Prof Craig Williams and my Director of Studies, Dr Clive Roberts, my mentor for the past four years for his constant encouragement and support, always optimistic and cheerful. Thank you for your support. It is a pleasure to thank the people who helped with different aspects of this Ph.D. especially, Dave Townrow, for helping with sampling and analysis, Diane Spencer, for ICP and IC analysis, Barbara Hodson, for SEM, Andy Black and Keith Thompson for their help in the chemistry laboratory, Andy Brooke, Bal and Ann Dawson for their help in microbiology, Wilma, Jen and Kate, the washing up ladies, Malc Inman and Colleen Delaney for their support and advice, David Luckhurst for his help with poster printing and GIS. Thanks also go to Fiona Bowers and Angie Williams, the laboratory managers who also helped with ordering and finance. Thanks to Sarah Lathe and Marie Bagley for the administrative help and for the long chats. I want to thank all the lecturers who gave me teaching opportunities; Dr Clive Roberts, Dr Dave Hill, Dr Terry Bartlett and Dr Chris Young, Dr Kate Farr, Dr Catherine Duke, Dave Williams, Dr Kate Tobin, Dr Lyn Besenyei, Dr Eleanor Cohn, for their contribution to my education, advice and support throughout this Ph.D. Thank you to Dr Iza Radecka for her help with the microbiology experiments. Thank you also to Dr Alison McCrea for her invaluable help and patience with the statistics. To the people in industry who have made this Ph.D. possible; Dr Helen Proffitt, Dr Paul Beckwith, Mike Youe (British Waterways), Dave Otterwell (Environment Agency), Dr Marc Cave and Dr Joanna Wragg (BGS), University of Coventry, De Monfort University and University of Birmingham for allowing me to use their equipment when I needed. My friends who have always supported me through the good and bad times over the past three years: Wan Li Low, Chris Crosby and Claara Ten Broek for all the good times. Thanks to my cousins and the long list of family members who have always encouraged me. Thanks to Chris Rogers, for his invaluable support during the past three years, for all your encouragement, competitiveness and fun times. I hope I have not missed anybody, my sincere apologies if I did; all of you have made this journey somewhat enjoyable and bearable during the hard times. Thank you! iv DEDICATION Finally, I cannot find the right words to express my utmost gratitude to my mother, Viga and father, Govind, who have supported me morally and financially throughout my life and my studies and who gave up everything to move to England and support me. My sister, Yovani, who has always believed in me and supported me. This thesis is dedicated to my Mother & Father, Viga & Govind v Table of Contents: ABSTRACT ............................................................................................................................................ III ACKNOWLEDGEMENTS .................................................................................................................... IV DEDICATION ......................................................................................................................................... V TABLE OF CONTENTS ......................................................................................................................... 2 TABLE OF EQUATIONS ....................................................................................................................... 8 TABLE OF TABLES ............................................................................................................................... 8 TABLE OF FIGURES ........................................................................................................................... 10 TABLE OF PLATES ............................................................................................................................. 13 LIST OF ABBREVIATIONS ............................................................................................................... 15 CHAPTER 1: INTRODUCTION ........................................................................................................ 17 1.1 WHY DREDGE SEDIMENTS? ......................................................................................................................... 17 1.2 CANALS ....................................................................................................................................................... 20 1.2.1 Canals in the UK .......................................................................................................................................... 20 1.2.2 Changing uses of canals .............................................................................................................................. 22 1.3 BRITISH WATERWAYS ................................................................................................................................. 22 1.4 REGULATIONS ............................................................................................................................................. 23 1.5 CLASSIFICATION OF DREDGED SEDIMENTS .................................................................................................