Durham E-Theses Heavy Metal Contamination Along the Coast of North-East England ALDERTON, SIMON,MARK How to cite: ALDERTON, SIMON,MARK (2012) Heavy Metal Contamination Along the Coast of North-East England, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/5918/ Use policy This work is licensed under a Creative Commons Attribution Non-commercial Share Alike 3.0 (CC BY-NC-SA) Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk University of Durham Faculty of Social Sciences & Health Department of Geography Heavy Metal Contamination Along the Coast of North-East England by Simon M. Alderton Thesis for the degree of Master of Science by Research March 2012 Abstract The last century has seen the north east coast of England heavily affected by an- thropogenic activities, none more notable than the coal mining industry, and the millions of tonnes of colliery waste estimated to have been dumped every year. Since the decline of the industry and subsequent remedial work carried out by the Turning the Tide Partnership, investigation of the coastline has been minimal. The purpose of this investigation is to consider the industrial forcing of the natural ecosystem which exists along the north east coast of England, and analyse the impacts of reme- diation in accelerating the recovery of the area from a state of economic exploitation, to natural habitat and environmental resource. Giusti et al. (1999) conducted a study which collected heavy metal data from the shell and tissue material of Mytilus edulis (the blue mussel) at five coastal locations along the north east of England, during the early stages of remediation (December 1997). A second study (Giusti, 2001) monitored the heavy metal contamination of Fucus vesiculosus (bladderwrack) along the coast during the same period. This investigation has provided comparative heavy metal data to these baselines, allowing assessments of the level of recovery to be made, while highlighting current areas of concern and the implications of post-remediation activity. The concentra- tions of Fe, Mn, Zn, Cr, Cu, Pb, Ni and Cd were determined in both the soft tissue and shell material of the blue mussel and common limpet (Patella vulgata) at sev- eral sites between Whitburn and the Tees estuary. Bladderwrack is included as a sensitive short term indicator of water based heavy metal contamination. Although the investigation finds that the long term metal contamination of the coastline has decreased, a change in the spatial pattern of pollution is observed, manifested by an increase in metal concentrations at the Tees estuary site of Bran Sands. The mobilisation and transport of offshore sediment is discussed as a possible causal factor. High levels of iron and manganese are recorded in all three indica- tors, suggesting an aqueous source. These high values include a 9-fold increase in iron contamination of bladderwrack (to ∼9,000 mg kg-1), and a 12-fold increase of manganese in bladderwrack at Roker estuary (to ∼1,600 mg kg-1). Subsequently, tentative links are drawn to the pumping of treated minewater into the sea at Horden and Dawdon. i Acknowledgements This work was undertaken with financial support from the Durham Heritage Coast Partnership and a tuition fees studentship from the University of Durham Geography Department. I would like to express my sincere gratitude to: • My supervisors, Dr. James Casford and Prof. Danny Donoghue, for their advice, guidance and support throughout the course of the study. • Niall Benson (Durham Heritage Coast Officer) and his team for providing funding, resources and an invaluable insight into the County Durham coastline. • Amanda Hayton, Martin West and Neil Tunstall for their time and effort in helping me prepare and analyse samples. • My Mother, for showing me there is a light at the end of the tunnel. ii Contents Abstract i Acknowledgements ii List of Figures vii List of Tables viii 1 Introduction 1 1.1 Evolution of the County Durham Coastline: From Coal Spoil to Her- itage Coast . 2 1.2 Introduction to the Sampling Sites . 5 1.2.1 Whitburn & Roker . 5 1.2.2 Dawdon, Easington, Horden & Blackhall Rocks . 5 1.2.3 Middleton, North Gare & Bran Sands . 5 1.3 The Remediation - Turning the Tide . 7 1.3.1 Since Turning the Tide, and Other Remediation . 8 1.3.2 Remediation of Estuarine Sources . 9 1.3.3 Implications . 10 1.4 Scientific Context . 10 1.5 The Current Study . 10 1.5.1 Aim . 11 1.5.2 Research Questions . 11 1.6 Monitoring Coastal Recovery . 11 1.7 Previous Studies of the County Durham Coastline . 13 1.8 Summary of Objectives . 14 2 Key Baseline Studies 15 2.1 \Biologically available trace metals in Mytilus edulis from the coast of north east England" (Giusti et al., 1999) . 15 iii 2.2 \Heavy metal contamination of brown seaweed and sediments from the UK coastline between the Wear river and the Tees river" (Giusti, 2001) . 16 2.3 Review . 18 3 Ecology 19 3.1 Rocky Shorelines . 19 3.2 Mytilus edulis ............................... 20 3.3 Patella vulgata .............................. 21 3.4 Fucus vesiculosus ............................. 22 3.5 Nucella lapillus .............................. 23 3.6 Heavy Metal Bioaccumulation . 23 4 Sample Preparation & Analytical Techniques 25 4.1 Digestion Techniques . 25 4.2 Analysis Techniques . 26 4.2.1 X-ray fluorescence (XRF) . 26 4.2.2 Atomic Absorption Spectroscopy (AAS) . 27 4.2.3 Inductively coupled plasma-mass spectroscopy (ICP-MS) . 27 4.3 Summary . 28 5 Introduction to Research 29 6 Heavy metal contamination in Mytilus edulis and Patella vulgata between the estuaries of the River Wear and River Tees, UK. 31 6.1 Abstract . 31 6.2 Introduction . 32 6.3 Methodology . 36 6.3.1 Ecological Consideration . 36 6.3.2 Legislative Values . 36 6.3.3 Sampling & Analysis . 38 6.3.4 Extraction & Measurement . 38 6.4 Results . 42 6.4.1 Shell Composition . 45 6.4.2 Tissue Data . 46 6.4.3 Variations in Type and Location of Contaminants . 47 6.4.4 Comparison with Legislative Values . 50 6.5 Discussion . 50 6.6 Conclusion . 52 iv 7 Monitoring the heavy metal contamination of the north east coast of England: a case study using the floral indicator, Fucus vesicu- losus. 53 7.1 Abstract . 53 7.2 Introduction . 54 7.3 Methodology . 57 7.3.1 Sampling and Analysis . 57 7.3.2 Extraction and measurement . 58 7.3.3 Faunal Samples . 59 7.4 Results . 60 7.4.1 Bioaccumulation . 68 7.4.2 High Fe and Mn Across Species . 70 7.5 Discussion . 71 7.6 Conclusion . 74 8 Conclusions 76 8.1 Reference to Research Questions . 76 8.1.1 What is the current spatial pattern of heavy metal contamina- tion in Mytilus edulis, Patella vulgata and Fucus vesiculosus along the County Durham coastline? . 76 8.1.2 What trends are observed between the data collected for each species? . 77 8.1.3 How do the current point concentrations and spatial trends compare to data collected prior to Turning the Tide? . 77 8.1.4 What impact could the process of remediation have had on the observed spatial and temporal trends? . 78 8.2 Further Discussion . 78 8.3 Future Work . 80 Bibliography 81 v List of Figures 1.1 Map showing designated land and former mine waste dumping sites . 3 1.2 Colliery spoil at Dawdon prior to mine closure . 4 1.3 Coastal sediment cells . 6 1.4 Nose's Point (Dawdon) post-remediation . 9 2.1 Map of study sites for the 1997 Fucus vesiculosus sample collection (after Giusti (2001)) . 17 3.1 Internal structure of the blue mussel, Mytilus edulis. After Morton (2005) . 21 3.2 Fucus vesiculosus (bladderwrack), (FSC, 2008) . 23 3.3 Predicted bioaccumulation of metals up the food chain . 24 6.1 GIS map of designated land, former coastal dumping sites, areas with treated minewater pumping, and study sites . 34 6.2 Metal Pollution Index (MPI) for shell material . 45 6.3 Metal Pollution Index (MPI) for tissue material . 46 6.4 Metal concentration values for Cr, Cd, Pb and Ni in tissue material of mussels and limpets . 48 6.5 Metal concentration values for Zn, Cu, Fe and Mn in tissue material of mussels and limpets . 49 7.1 Map showing Heritage Coast designated land, former mine waste dumping sites, and Fucus vesiculosus sample collection sites. 55 7.2 Metal Pollution Index (MPI) for Fucus vesiculosus . 62 7.3 Fe concentrations (mg kg-1) in bladderwrack before and after reme- diation . 63 7.4 Mn concentrations (mg kg-1) in bladderwrack before and after reme- diation . 63 7.5 Cu concentrations (mg kg-1) in bladderwrack before and after reme- diation . 64 7.6 Zn concentrations (mg kg-1) in bladderwrack before and after reme- diation . 64 vi 7.7 Pb concentrations (mg kg-1) in bladderwrack before and after reme- diation . 65 7.8 Cd concentrations (mg kg-1) in bladderwrack before and after reme- diation . 65 7.9 Cr concentrations (mg kg-1) in bladderwrack before and after reme- diation . 66 7.10 Ni concentrations (mg kg-1) in bladderwrack before and after reme- diation . 66 7.11 EA monitoring of treated minewater effluent at Dawdon . 72 7.12 EA monitoring of treated minewater effluent at Horden . 73 vii List of Tables 6.1 National and international guidelines/limits for metal contamination of shellfish . 37 6.2 Recovery of metals in certified reference material IAEA-413 (Algae) . 40 6.3 Repeat digestion and analysis of a single sample from the study, in- cluding mussel shell and tissue data .