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The Critical Raw Materials Potential of Anthropogenic Deposits Insights from Solid Residues of Municipal Waste Incineration

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The Critical Raw Materials Potential of Anthropogenic Deposits Insights from Solid Residues of Municipal Waste Incineration Alma Mater Studiorum – Università di Bologna DOTTORATO DI RICERCA IN Scienze della Terra Ciclo XXVIII Settore Concorsuale di afferenza: 04/A1 Settore Scientifico disciplinare: GEO/08 TITOLO TESI The critical raw materials potential of anthropogenic deposits insights from solid residues of municipal waste incineration Presentata da: Valerio Funari Coordinatore Dottorato Relatore Jo Hilaire Agnes De Waele Roberto Braga Esame finale anno 2016 II III IV Preface The present thesis is the result of a PhD project carried out at the Doctoral School on Earth Sciences of the University of Bologna. Dr. Roberto Braga (BiGeA Dept., University of Bologna) acted as supervisor of the PhD project titled “The critical raw materials potential of anthropogenic deposits: insights from solid residues of municipal waste incineration”. Journal manuscripts prepared during this study are enclosed: 1. Funari V., Braga R., Bokhari N., Dinelli E., Meisel T. (2015). Solid residues from incinerators: a source for Critical Raw Materials. Waste Management, 45: 206-216. 2. Funari V., Bokhari N., Vigliotti L., Meisel T., Braga R (2016). The Rare Earth Elements in Municipal Solid Waste Incinerators ash and promising tools for their prospecting. Journal of Hazardous Materials, 301, p. 471-479. 3. Funari V., Mäkinen J., Salminen J., Braga R., Dinelli E., Revitzer H. Metal Recovery from Municipal Solid Waste Incinerators Fly Ash: a Preliminary Comparison between Chemical Leaching and Bioleaching. Submitted to Waste Management 4. Funari V., Meisel T., Braga R. (2015). The potential impact of municipal solid waste incinerators ashes on the anthropogenic osmium budget. Science of the Total Environment, 541: 1549-1555. The above scientific articles, peer-reviewed or awaiting for decision, are reported as in their original version but with the text formatting of the present thesis. In addition, ten publications in proceedings have been accomplished during the study and their abstracts are enclosed in Appendix A. V VI Acknowledgements The University of Bologna, the Spinner Consortium and extramural support by Prof. Giovanni Gabbianelli jointly funded the study. The regional funds by the Spinner Consortium come from the project “MAPPER-Materie Prime Essenziali per l’Emilia Romagna” awarded to Dr. Roberto Braga (principal investigator), Dr. Giuseppe Maria Bargossi, Dr. Enrico Dinelli, Dr. Giovanni Gabbianelli, Dr. Paolo Garofalo, Dr. Giorgio Gasparotto (University of Bologna), Dr. Gianluca Bianchini (University of Ferrara), Dr. Daniele Brunelli (University of Modena and Reggio Emilia), Dr. Sandro Meli, Dr. Alessandra Montanini, Dr. Mario Tribaudino, Dr. Teresa Trua (University of Parma). The final purpose of the MAPPER project was the formation of an expert in the field of applied mineralogy and geochemistry, ore geology, waste management, and mineral processing. Furthermore, the PhD project benefited of visiting fellowships supported by the Marco Polo programme (University of Bologna) that allowed the following research visits: Montanuniversität Leoben (Austria, 4 months) and the VTT- Technical Research Centre (Finland, 3 months). Thomas Meisel (Chair at General and Analytical Chemistry, Montanuniversität Leoben) and Justin Salminen (Senior Researcher at Boliden, formerly at VTT), are warmly thanked for their support during these successful visiting periods. External referees Dr. Roberta Bertani, Dr. Päivi Kinnunen, Dr. Jakob Lederer, Dr. Oumaya Yazoghli-Marzouk, and Dr. Alessandra Polettini are gratefully acknowledged for the proofreading of this thesis and valuable suggestions. VII VIII Table of Contents Abstract ...................................................................................................................... 2 Structure of the work................................................................................................ 6 List of Abbreviations ................................................................................................ 8 List of Figures .......................................................................................................... 12 List of Tables ............................................................................................................ 16 Chapter 1 Introduction to the thesis work............................................................................. 20 1. More than waste............................................................................................. 21 1.1 Critical Raw Material ................................................................................ 23 1.2 The rare earth elements ............................................................................ 25 1.3 The platinum group elements with emphasis on osmium ................. 26 2. Driving-question and issues......................................................................... 29 2.1 Main issues ................................................................................................. 30 3. Municipal solid waste incinerators and their solid residues ................... 32 3.1 Bottom ash .................................................................................................. 33 3.2 Fly ash ......................................................................................................... 34 3.3 Mineralogy of MSWI residues ................................................................ 35 4. Samples collection ......................................................................................... 38 5. Methods........................................................................................................... 39 5.1 Geochemical methods .............................................................................. 39 5.1.1 Sample preparation and efforts for reliable XRF data .................. 40 5.1.2 The sodium peroxide sintering technique ...................................... 43 5.1.3 Isotope dilution with High Pressure Asher acid digestion ......... 45 5.1.4 Other analytical methods .................................................................. 48 5.2 Strategic tools for prospecting: Substance flow analysis ..................... 48 5.3 Magnetisation and magnetic methods ................................................... 49 5.4 Methods for separation, upgrading and treatment .............................. 50 5.4.1 Overview on physical-mechanical separation methods .............. 51 5.4.2 Chemical separation: bio-hydrometallurgy ................................... 52 5.4.3 Leaching and leachability ................................................................. 53 References ........................................................................................................... 55 Chapter 2 Solid residues from Italian municipal solid waste incinerators: a source for “critical” raw materials .......................................................................................... 62 Abstract ............................................................................................................... 63 1. Introduction .................................................................................................... 65 IX 2. Materials and methods .................................................................................. 67 2.1 Bottom and fly ash samples ..................................................................... 67 2.2 Sampling and sample preparation .......................................................... 68 2.3 Analytical techniques ................................................................................ 71 2.3.1 X-ray fluorescence spectrometry ...................................................... 72 2.3.2 Inductively coupled plasma spectrometry ..................................... 72 2.4 Substance flow analysis ............................................................................ 74 3. Results and discussion .................................................................................. 76 3.1 Bottom ash .................................................................................................. 76 3.1.1 Gravitative control on partitioning of critical elements................ 80 3.2 Fly ash ......................................................................................................... 81 3.3 Estimated annual flow of SWI-1 residues .............................................. 84 3.4 Transfer coefficients of SWI-1 residues .................................................. 87 3.5 “Urban” deposits as potential target for raw materials supply .......... 89 5. Conclusions ..................................................................................................... 92 Acknowledgements ........................................................................................... 93 References ........................................................................................................... 93 Supplementary Materials of Chapter 2 ......................................................... 100 S.1 Effectiveness of a stratified random method ....................................... 100 S.2 The calculation of transfer coefficients ................................................. 102 Chapter 3 The Rare Earth Elements in Municipal Solid Waste Incinerators ash and promising tools for their prospecting ................................................................. 104 Abstract ................................................................................................................... 105
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