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Laurence Kavanagh Phd Thesis 2018.Pdf (8.375Mb) Comparative Hydro-geochemistry: Distribution of Metal Ions in Groundwater, Surface Water, Soils and Plants in the South East of Ireland. By Laurence Kavanagh A Thesis presented for the Degree of Doctor of Philosophy Submitted to the Institute of Technology, Carlow Supervisors: Mr Jerome Keohane; Dr Guiomar Garcia-Cabellos; Dr Andrew Lloyd; and Dr John Cleary. External Examiner: Dr Teresa Curtin Internal Examiner: Dr Kieran Germaine i DECLARATION I certify that this thesis, submitted in line with the requirements for the award of PhD, (Philosophiae doctor) is entirely my own work 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. This thesis was prepared according to the regulations for postgraduate study by research of the Institute of Technology Carlow and has not been submitted in whole or in part for an award in any other Institute or University. The work reported in this thesis conforms to the principles and requirements of the Institute's guidelines for ethics in research. Signature ___________________________Date _______________ i Dedication: For my beautiful fiancée Sarah and my children Holly and Jacob. “Remember life is what happens while you’re busy” ii Acknowledgements This work would not have been possible without the assistance of many people and is the culmination of countless pep talks and the occasional dressing down. To my supervisor Dr Andrew Lloyd, I owe an enormous debt of gratitude for all the times you have patiently guided me through a swamp of statistics, purple prose, and for your ability to rein in my lofty ideas. For my other long-suffering supervisor Dr John Cleary, I am grateful for your cool-headed advice and patience. I will be forever thankful to my supervisor Dr Guiomar Garcia Cabellos, you provided me with a realist approach and solid base that was very important to me. For my supervisor Mr Jerome Keohane, I have to thank for your real-world advice and the important opportunities that you have provided me. Special thanks go to all in EnviroCORE. I am also grateful to Mr John Harrop of Blackstairs Lithium Ltd, for his constructive comments. A massive thank you to my pal Christopher Finnegan, without you my time in college would have been way more productive but less fun, so thanks. Most importantly I would like to thank my family for their support. Holly and Jacob, without the two of you, I wouldn’t have come through the educational wringer with the same disposition I had going in. The person I have to thank the most is my fiancée Sarah, whose support and positive outlook through the years have been incredible. iii Funding Acknowledgement This study was carried out at EnviroCORE, Department of Science and Health, Institute of Technology Carlow, Ireland. We acknowledge support from the Institute of Technology Carlow President’s Research Fellowship Programme fund and the Development and Research Postgraduate fund from the Institute. We also acknowledge support from the Irish Environmental Protection Agency through the Irish Research Council postgraduate funding scheme. iv Table of Contents List of tables…………………………………………………………….…….....viii List of figures……………………………………………………………………...x Structure of thesis…………………………………………………….………….xiii Safety protocol………………………………………………………………..…xiv Abbreviations……………………………………………………………….……xv Abstract……………………………………………………………………………1 General introduction………………………………………………………...……..2 Chapter 1: Global Lithium Sources, Industrial Use and Future in the Electric Vehicle Industry: A Review 1.1. Abstract…………………………..………………………………….…….....5 1.2 Introduction……………….……………………………………………..…...6 1.2.1. Methodology…………………………………………...…………....9 1.2.2. Lithium…………………………………………................................9 1.3 Lithium in the Environment………..……………………………………....11 1.3.1. Lithium in Water………..…………………………………...……....11 1.3.2. Lithium in Soil………………...………………………………..…....12 1.3.3. Lithium Industrial Resources…….………………………………...14 1.3.4. Lithium in Brines…………………………………………………...18 1.3.5 Lithium in Minerals………………………………………………...22 1.3.6. Lithium Mining and the Environment…………………………...…33 1.4 Lithium Uses…………………………………………………………………35 1.4.1. Glass and Ceramics……………………………………………..….36 1.4.2. Lithium as a Desiccant…………………………….…………..…..37 1.4.3. Organolithium Chemistry………………………….…….….….….37 1.4.4. Lithium as a Lubricant…………………………….….……..….….38 1.4.5. Lithium in Medicine………………………………..…….……..…..39 1.4.6. Lithium in Warfare…………………………………...….……..…..42 1.4.7. Metallurgy……………………………………………………...….43 1.4.8. Lithium Batteries……………………………………………….…..44 1.4.9. Lithium Recycling………………………………….…………...….49 1.5 Discussion…………………………….……………………………..……….50 v 1.6 Conclusion………………………………………………………………...…52 Chapter 2: Lithium in the Natural Waters of the South East of Ireland 2.1 Abstract……………………………………………………………………...55 2.2 Introduction....................................................................................................56 2.3 Materials and Methods...................................................................................60 2.3.1. Sampling…………………………………………………………...60 2.3.2. Surface Water Sampling…...………………………………………62 2.3.3. Groundwater Sampling…………………………………………….62 2.3.4. Sample Preparation……………...…………………………...…...63 2.3.5. Reagents……………………...…………………………….…...……63 2.3.6. Analysis……………………………………………………………63 2.3.7. Interference…………………..…………………………………....64 2.3.8. Data Analysis……………………………………………………………..64 2.4 Results………………...…….………………………......................................65 2.4.1. Statistical Analysis………………………………..……….……….65 2.4.2. Bimonthly Data.................................................................................66 2.4.3. Additional Metals………………..………………….…………...…72 2.5 Discussion……………………………….……………………………..….…73 2.6 Conclusion…………………………………………………………………...75 Chapter 3: Lithium in the Soils and Plants of the South East of Ireland 3.1 Abstract…………………………………..……….………………….……...77 3.2 Introduction……………………………………………………………..…..78 3.2.1. Lithium……………………………………………….…………….79 3.2.2. Lithium Globally…………………………………….……………..80 3.2.3. Lithium in the South East of Ireland………………………….……81 3.2.4. Lithium in Soil……………………………………………..……….81 3.2.5. Lithium in Plants…………………………………………..……….84 3.3. Materials and Methods…………………………………………………......86 3.3.1. Reagents…………………………………………………………...86 3.3.2. Sampling…………………………………………………………...86 3.3.3. Sampling Preparation……………………………….……………..86 3.3.4. Analysis……………………………………………………....……87 vi 3.4 Discussion and Results……………………………………………...………88 3.4.1. Lithium, pH and Conductivity in Soil………………………………88 3.4.2. Lithium in Ash and Ivy……………………………………..….…....88 3.4.3. Accessory Metal Concentration in Soils and Plants ……..…….…89 3.4.4. Analysis………………………………..………………………......90 3.5 Conclusion……………………………………………………………..…….94 Chapter 4: Induced Plant Accumulation of Lithium 4.1 Abstract………………………………………………………………..…….97 4.2 Introduction……………………………………………………..…………..98 4.3 Materials and Methods………………………………………………….....104 4.3.1. Reagents………………………………………………………….104 4.3.2. Germination Trials………………………………………………..105 4.3.3. Soil Preparation……………………………………………….….106 4.3.4. Plant trials………………………………………………………...106 4.3.5. Sample Preparation and Analysis………………………………....108 4.3.6. Data Analysis……………………………………………………..109 4.4 Discussion and Results……………………………………………………..109 4.4.1. Germination Trial Data………………………………………..….109 4.4.2. Plant Pot Trials……………………………………………………109 4.4.3. Trial 1, Lithium Amended Soil………………………………..….110 4.4.4. Trial 2, Lithium Amended oil, EDTA Treatment…………………113 4.4.5. Trial 3, Lithium Amended oil, EDDS Treatment…………………115 4.5 Conclusion……………………………………………………………….…118 Chapter 5: Synopsis and future perspectives 5.1 Conclusion……………………………………………...………………………121 5.2 Future perspectives………………………………………………...…………...123 Chapter 6: Dissemination of the thesis 6.1 Scientific journal publications……………………………………………….…126 6.2 Conference presentation…………………………………………………….…126 7. Appendix………………………………………………………………...128 7.1 Sampling point GPS data………………………………………………...…...….128 vii 7.2 Water heat data maps……………………………………………...…………..…129 7.3 Soil heat data maps……………………………………………………...………..135 7.4 Plant heat data maps………………………………………………………….......138 7.5 Germination trial data……………………………………………………………144 7.6 Supplementary agro-mining data………………………………………………....145 8. References…………………………….…………………………………146 List of tables Table 1.1. Lithium concentrations in seawater given in the literature, units – mg/l………………………………………………………………..7 Table 1.2. Lithium's average crustal abundance, units – mg/kg lithium……………………………………………………………..8 Table 1.3. Lithium concentrations in various rocks, units – mg/kg………….12 Table 1.4. Lithium concentration in different soils, units – mg/kg…………..13 Table 1.5. Global lithium resource estimates, units – Mt (megatons)………..13 Table 1.6. Estimates of global lithium resources by country from the literature. Units – Mt (megatons), (D.R. Congo – Democratic Republic of Congo)…………………………………………………………....14 Table 1.7. Location and parameters of some of the main lithium-containing brines …………………………………………………………….17 Table 1.8. List of 145 named lithium minerals and Li2O percentage………..17 Table 1.9. Location and parameters of some lithium pegmatites mines globally. ……………………………………………………………………21 Table 1.10. Comparison between current LIB technologies and previous battery technology………………………………………………………..24 Table 1.11. Location and parameters of some lithium pegmatites mines globally…...29 viii Table 1.12 Comparison between current LIB technologies and previous battery
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