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TABLE OF CONTENTS Page Copyright; List of additional volumes of Reviews in Mineralogy ii Foreword; Preface and Acknowledgments iii Chapter 1 G. D. Guthrie, Jr. & B. T. Mossman MERGING THE GEOLOGICAL AND BIOLOGICAL SCIENCES: AN INTEGRATED APPROACH TO THE STUDY OF MINERAL-INDUCED PULMONARY DISEASES Introduction 1 References 5 Chapter 2 C. Klein ROCKS, MINERALS, AND A DUSTY WORLD Introduction 7 Some Mineralogical Background 9 General references 9 Quantitative characterization of mineral particles in dust 10 Chemical variation in minerals 10 Chemical characterization of dust particles 13 Examples of Potentially Hazardous Minerals in Dust 14 Amphiboles 14 Chrysotile 17 Other layer silicates 19 Kaolinite 20 Vermiculite 21 Montmorillonite 21 Talc 22 Muscovite 22 Chlorite 23 Sepiolite and palygorskite 25 Silica (Si02) group 25 Zeolite group 27 Roggianite 29 Mazzite 30 Erionite 30 Mordenite 31 Natural Dusts 32 Generation and migration of natural dusts 32 The hydrologic cycle and weathering processes 32 Erosion rates and source areas of natural dust 35 Wind action 37 Short distance eolian transport 39 Long distance eolian transport 39 Volcanic activity 41 Determination of the background levels of natural dusts 42 Lung particulate burdens 42 v Global background level for fiber counts in the troposphere 44 Measurements from fluvial sources 46 Dust from Antarctic ice cores 47 The geology of two major natural fiber sources 49 New Idria (Coalinga) chrysotile region, California 49 Riebeckite and crocidolite in the Hamersley Range of Western Australia 52 Concluding Remarks 54 Acknowledgments 56 References 56 Chapter 3 D. R. Veblen & A. G. Wylie MINERALOGY OF AMPHIBOLES AND 1:1 LAYER SILICATES Introduction 61 Existing review literature 61 Crustal Elemental Abundances, Structure Determination, and Representation of Silicate Mineral Structures 63 Crustal abundance of the chemical elements 63 Determination and refinement of crystal structures 63 Coordination structure and their representation in two and three dimensions 64 Polymerization in silicates 66 Mineral Habit 67 Asbestos and the asbestiform habit 69 Cleavage and parting 71 1:1 Layer Silicates 71 Basic 1:1 layer structure 71 Nomenclature 73 Geological occurrence of 1:1 layer silicates and associated minerals 74 Serpentine group 74 Kaolin group 75 Other 1:1 layer silicates 76 Crystal structures and chemistry of the serpentine group 76 Lizardite 77 Layer conformation 77 Polytypism and symmetry 77 Chemical variations 78 Chrysotile 78 Layer conformation 78 Chrysotile polymorphs and polytypes 80 Chemical variations 81 Antigorite 81 Layer conformation 81 Structural disorder and defects in antigorite 83 Polytypism and chemical variations 83 Carlosturanite 84 Polygonal serpentine 84 Serpentine intergrowths and other hybrid serpentine structures 84 Crystal structures and chemistry of the kaolin group 85 Kaolinite, dickite, and nacrite 85 Layer conformation 87 Layer stacking, octahedral vacancy distribution, and hyd rogen bonding 87 Structural disorder in kaolinite 88 vi Chemical variations 90 Halloysite 90 Layer conformation 90 Layer stacking and other structural details 90 Crystal structures of other 1:1 layer silicates 91 Amesite and kellyite 91 Berthierine, brindleyite, and fraipontite 91 Odinite 92 Cronstedtite 92 Nepouite and pecoraite 92 Habit of 1:1 layer silicates 92 Serpentine-group minerals 92 Kaolin-group minerals 94 Other 1:1 layer silicates 94 Surface chemistry, surface charge, and dissolution kinetics of chrysotile... 95 Surface chemistry and structure 95 Surface charge 97 Dissolution kinetics 97 Amphiboles 100 Basic structure, chemistry, and nomenclature 100 Geological occurrence of amphiboles 101 Amphibole crystal structure types 102 Clinoamphiboles 103 Polyhedral distortions and rotations 103 Space-group symmetry 104 Orthoamphiboles 105 Protoamphibole 105 The biopyribole polysomatic series and ordered pyriboles related to amphibole 105 Defects and grain boundaries in amphiboles 107 Chain-width errors 107 Twinning 108 Stacking faults 108 Dislocations 108 Exsolution lamellae 109 Grain boundaries 109 Compositional variations in amphibole asbestos 109 Crystallization, mineralogy, and structure of amphibole asbestos and other amphibole habits 110 Asbestiform amphibole 110 Byssolite and nephrite 116 Cleavage and parting fragments of nonasbestiform amphiboles 116 Dimensions of amphibole fibers and cleavage fragments 116 Surface chemistry, surface charge, and dissolution kinetics of amphibole asbestos 117 Surface chemistry and structure 117 Surface charge 119 Dissolution kinetics 119 Implication of 1:1 Layer Silicates, Amphiboles, and Wide-Chain Pyriboles 120 Optical microscopy (OM) 120 Kaolin 120 Serpentine 120 Amphiboles and wide-chain pyriboles 121 X-ray diffraction (XRD) 122 1:1 layer silicates 122 Amphiboles and wide-chain pyriboles 123 Scanning electron microscopy (SEM) and electron microprobe analysis 123 vii The scanning electron microscope 123 Quantitative and qualitative chemical analysis in the SEM 124 Electron microprobe analysis 125 Identification of 1:1 layer silicates and asbestos with the SEM 125 Transmission electron microscopy (TEM) methods for asbestos identification 126 Chrysotile asbestos 127 Amphibole asbestos 127 Analysis of asbestos in bulk samples 128 Analysis of asbestos in air samples and lung burden 130 Acknowledgments 130 References 131 Chapter 4 D. L. Bish & G. D. Guthrie, Jr. MINERALOGY OF CLAY AND ZEOLITE DUSTS (EXCLUSIVE OF 1:1 LAYER SILICATES) Introduction 139 Hydroxides 142 Geological occurrence 142 Crystal chemistry 142 Crystal structures 143 Microstructures and morphologies 145 Surface properties 146 Adsorption characteristics 148 2:1 Layer Silicates 149 Geological occurrence 149 Crystal chemistry 150 Crystal structures 154 Microstructures and morphologies 160 Surface properties (potentially active surface sites) 160 Catalytic properties 161 Chain-structure Layer Silicates 162 Geological occurrence 162 Common associated minerals 162 Crystal chemistry 162 Crystal structures 163 Microstructures and morphologies 165 Surface properties 166 Exchange characteristics 167 Uses 167 Zeolites 168 Geological occurrence 168 Crystal chemistry 169 Crystal structure 172 Morphologies 178 Molecular sieving, exchange, and catalytic properties 179 References 181 viii Chapter 5 P. J. Heaney & J. A. Banfield STRUCTURE AND CHEMISTRY OF SILICA, METAL OXIDES, AND PHOSPHATES Introduction 185 The Silica System 186 Phase equilibria and geological occurrences 186 Crystalline silica 186 Amorphous silica 188 Phase stability 190 Silica: Applications and regulations 190 Uses 190 Restrictions 191 Structures of the silica polymorphs 194 Quartz 194 Microcrystalline quartz 195 Tridymite and cristobalite 197 Coesite and stishovite 200 Amorphous silica 200 Impurity elements 202 Solubilities and surface structure 203 Interactions between organic molecules and silica 205 Carcinogenicity of silica 206 Geochemistry of Iron and Titanium Oxides 206 Introduction 206 The Ti02 system 208 Occurrence and commonly associated minerals 208 Crystal structures 209 Rutile 209 Brookite and anatase 209 Ti02(B) 209 Trace element chemistry and defect microstructures 211 Particle morphology 212 Potentially active surface sites 212 Solubility 216 Iron oxides and iron-titanium oxides 216 Occurrence and commonly associated minerals 217 Crystal structures 218 Hematite (a-Fe203) and ilmenite 218 Magnetite and iilvospinel 219 Maghemite and titanomaghemite 220 Wustite 220 Trace element chemistry and defect microstructures 220 Particle morphology 221 Potentially active surface sites 221 Solubility 222 Phosphates 223 Acknowledgments 224 References 225 ix Chapter 6 S. J. Chipera, G. D. Guthrie, Jr. & D. L. Bish PREPARATION AND PURIFICATION OF MINERAL DUSTS Introduction 235 Sources for Mineral Specimens 236 Preparation of Mineral Dust Specimens 236 Disaggregation 236 Purification 237 Sieving 237 Magnetic separation 237 Density separation 238 Separation based on settling velocity 240 Combined separation techniques 243 Size fractionation 244 Summary 245 References 246 Appendix 1 246 Mineral specimens 246 Equipment/Supplies 247 Appendix II 247 Principle 247 Equipment and materials 247 Methodology 248 Chapter 7 G. D. Guthrie, Jr. MINERAL CHARACTERIZATION IN BIOLOGICAL STUDIES Introduction 251 Mineral species 254 Mineral Content 255 X-ray diffraction 255 Transmission electron microscopy 260 Mineral Structures 260 Deviations from ideal structure 261 Mineral Compositions 261 Electron probe microanalysis 261 Analytical electron microscopy 266 PIXE and SIMS 267 Proton-induced X-ray emission (PIXE) 267 Secondary ion mass spectrometry (SIMS) 268 Mineral Surfaces 268 Surface structure 269 Scanning electron microscopy 269 Scanning probe microscopies 269 Low energy electron diffraction 269 Transmission electron microscopy 270 Determination of surface composition 270 Acknowledgments 270 References 270 x Chapter 8 M. F. Hochella, Jr. SURFACE CHEMISTRY, STRUCTURE, AND REACTIVITY OF HAZARDOUS MINERAL DUST Introduction 275 The General Nature of Mineral Surfaces 276 Surface composition 277 Surface atomic structure 278 Surface microtopography 279 Surface charge 282 Relationship between Mineral Surfaces and Their Biological Activity 284 Evidence for activity dependence on surface composition 284 Evidence for activity dependence on surface atomic structure 286 Evidence for activity dependence on surface microtopography 287 Evidence for activity dependence on surface charge 288 The Surfaces of Chrysotile and Crocodolite 289 Chrysotile 289