Crystal Chemistry of Cadmium Oxysalt and associated Minerals from Broken Hill, New South Wales Peter Elliott, B.Sc. (Hons) Geology and Geophysics School of Earth and Environmental Sciences The University of Adelaide This thesis is submitted to The University of Adelaide in fulfilment of the requirements for the degree of Doctor of Philosophy September 2010 Table of contents Abstract.......................................................................................................................vii Declaration................................................................................................................ viii Acknowlegements........................................................................................................ix List of published papers ..............................................................................................x Chapter 1. Introduction ..............................................................................................1 1.1 General introduction ............................................................................................1 1.2 Crystal Chemistry ................................................................................................2 1.2.1 Characteristics of Cadmium..........................................................................3 1.2.2 Characteristics of Lead .................................................................................4 1.2.3 Characteristics of Selenium ..........................................................................5 1.2.4 Characteristics of Zinc ..................................................................................5 1.2.5 Characteristics of Copper..............................................................................6 1.2.6 Characteristics of Arsenic.............................................................................7 1.3 Solid solution in minerals ....................................................................................7 1.4 The Stability of Minerals .....................................................................................8 1.5 References..........................................................................................................13 Chapter 2. Experimental...........................................................................................18 2.1 Sample acquisition.............................................................................................18 2.2 Single-crystal X-ray Diffraction ........................................................................18 2.3 Electron-microprobe analysis ............................................................................20 2.4 X-ray powder diffraction ...................................................................................20 2.5 Other instrumental techniques ...........................................................................20 2.6 References..........................................................................................................21 Chapter 3. The crystal structure of munakataite ...................................................24 Abstract....................................................................................................................26 3.1 Introduction........................................................................................................26 3.2 Chemical Composition.......................................................................................27 3.3 Infrared Spectroscopy ........................................................................................28 3.4 Structure Determination.....................................................................................29 3.5 Structure Description .........................................................................................35 3.5.1 Cation coordination.....................................................................................35 3.5.2 Structure topology.......................................................................................38 ii 3.6 Bond Valence Calculations and Hydrogen Bonding .........................................40 3.7 Structural Relations............................................................................................43 3.8 Acknowledgements............................................................................................43 3.9 References..........................................................................................................43 Chapter 4. Description and crystal structure of a new mineral, edwardsite, Cu3Cd2(SO4)2(OH)6·4H2O, from Broken Hill, New South Wales, Australia........48 Abstract....................................................................................................................50 4.1 Introduction........................................................................................................50 4.2 Occurrence .........................................................................................................51 4.3 Appearance, Physical and Optical Properties ....................................................51 4.4 Chemical Composition.......................................................................................52 4.5 Infrared Spectroscopy ........................................................................................52 4.6 X-Ray Powder Diffraction Data ........................................................................53 4.7 Structure Determination.....................................................................................53 4.7.1 Single-crystal X-ray data collection............................................................53 4.7.2 Structure solution and refinement...............................................................54 4.8 Structure Description .........................................................................................55 4.8.1 Cation coordination.....................................................................................55 4.8.2 Structure connectivity .................................................................................59 4.9 H2O and OH groups and hydrogen bonding......................................................59 4.10 Structural Relations..........................................................................................61 4.11 Acknowledgements..........................................................................................63 4.12 References........................................................................................................63 Chapter 5. The crystal structure of cadmian serpierite from the Block 14 Opencut, Broken Hill, New South Wales.................................................................65 Abstract....................................................................................................................67 5.1 Introduction........................................................................................................67 5.2 Infrared Spectroscopy ........................................................................................69 5.3 Chemical Composition.......................................................................................69 5.4 Single-crystal X-Ray Diffraction.......................................................................72 5.5 Stucture Description...........................................................................................79 5.5.1 Cation coordination.....................................................................................79 5.5.2 Stucture topology........................................................................................83 5.6 H2O and OH groups and hydrogen bonding......................................................85 iii 5.7 Relationships to other Minerals .........................................................................88 5.8 Acknowledgements............................................................................................89 5.9 References..........................................................................................................90 Chapter 6. The crystal chemistry of gartrellite group minerals from the Kintore Opencut, Broken Hill, New South Wales.................................................................94 Abstract....................................................................................................................96 6.1 Introduction........................................................................................................97 6.3 Chemical Analysis .............................................................................................98 6.2 Infrared Spectroscopy ......................................................................................108 6.4 Structure Solution and Refinement..................................................................109 6.5 Description of the Structure.............................................................................115 6.6 Hydrogen Bonding...........................................................................................120 6.7 Structural Relations..........................................................................................122 6.8 Acknowledgements..........................................................................................124 6.9 References........................................................................................................124 Chapter 7. 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