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 General surface description 289 Surface site character and surface charge 290 Surface site reactivity 291 Dissolution behavior 292 Implications for biological activity 292 Crocidolite 293 General surface description 293 Surface site character and surface charge 296 Surface site reactivity 296 Dissolution behavior 297 Implications for biological activity 299 Treatment with deferoxamine 300 Summary and Conclusions 303 Acknowledgments 305 References 305

Chapter 9 R. P. Nolan & A. M. Langer

LIMITATIONS OF THE STANTON HYPOTHESIS

Introduction 309 Early Experimental Animal Studies Relating Fiber Morphology to Carcinogenicity 310 Dosimetry of fibers 316 Conclusions of the implantation studies 319 Limitations of the Stanton hypothesis 321 References 325

Chapter 10 R. F. Giese, Jr. & C. J. van Oss

THE SURFACE THERMODYNAMIC PROPERTIES OF SILICATES AND THEIR INTERACTIONS WITH BIOLOGICAL MATERIALS

Introduction 327 Surface Thermodynamic Theory 328

xi Surface tension, interfacial tension and surface free energies 328 The apolar component 329 The polar component 329 Free energy of adsorption 330 Contact angles and the Young equation 331 Powdered materials and the Washburn equation 333 Hydrophobic and hydrophilic surfaces 334 Electrostatic Interactions 335 ¡¡-potential 335 Total interaction energy between two particles 336 Surface Tension of Minerals and Related Materials 336 Asbestos 337 Sepiolite and palygorskite 338 2:1 layer silicates 339 Smectite 339 Muscovite and illite 339 Talc and pyrophyllite 340 Quartz 340 Glass, natural and synthetic 340 Effects of Surface-Sorbed Organic Material 341 Surface Properties of Biological Materials 342 Interactions Between Mineral Surfaces and Biological Materials 342 Average non-specific repulsion 343 Discrete site attraction 343 Low energy surfaces 344 References 344

Chapter 11 A. B. Kane

EPIDEMIOLOGY AND PATHOLOGY OF ASBESTOS-RELATED DISEASES

Historical Introduction 347 Key Epidemiologic Studies of Asbestos-related Diseases 348 Major diseases associated with asbestos exposure 348 Studies in occupational epidemiology of asbestos-related diseases 349 Case series 349 Case control studies 349 Cohort studies 350 Limitations of epidemiologic studies 352 Clinical and Pathologic Features of Asbestos-related Diseases 352 Pulmonary diseases 352 Asbestosis 352 Lung cancer 353 Pleural reactions 353 Other diseases associated with asbestos exposure 354 Pathogenesis of asbestos-related diseases 354 Implications of epidemiologic studies for prevention of asbestos- related diseases 356 Acknowledgments 358 References 358

xii Chapter 12 M. Ross, R. P. Nolan, A. M. Langer & W. C. Cooper

HEALTH EFFECTS OF MINERAL DUSTS OTHER THAN ASBESTOS

Introduction 361 The Silica Minerals and Amorphous Silica 362 Mineralogy of silica 362 Diseases related to exposure to silica dust 363 Silicosis 363 Silicotuberculosis 364 Cancer 364 Epidemiological studies of occupational cohorts exposed to crystalline silica dust 366 Minnesota iron ore miners (magnetite-bearing rock) 366 Iron ore miners (hematite-bearing rock) 369 European iron ore miners 370 Gold miners (South Dakota) 371 Gold miners (Kalgoorlie, Western Australia) 375 Granite workers (Vermont) 375 Slateworkers (Vermont, North Wales, and Germany) 377 Diatomaceous earth workers 378 Sandblasting 381 Cohort studies of certified silicotics 381 Coal 383 Mineralogy 383 Diseases related to exposure to coal dust 383 Coal workers' pneumoconiosis 383 Coal workers' silicosis 384 Epidemiological studies of occupational cohorts exposed to coal dust 384 Pneumoconiosis mortality and morbidity 385 Cancer mortality 385 The Silicate Minerals (Other than Asbestos) 386 Mineralogy of the silicates 386 Health effects of selected silicate minerals 387 Talc and pyrophyllite 387 Kaolinite 388 Bentonite 388 Palygorskite/attapulgite and sepiolite 388 Micas 390 Vermiculite 390 Wollastonite 394 Zeolites 394 Environmental Exposures to Fibrous Minerals 394 Environmental exposure to mineral fiber in Turkey, Cyprus, and Greece. .394 Fibrous zeolites and the Karain experience 396 Experimental animal studies corroborate the human studies 398 References 401

Chapter 13 A. Churg

ASBESTOS LUNG BURDEN AND DISEASE PATTERNS IN MAN

Introduction 410 Analytical Methods 410

xiii The Relationship between Physical/Chemical Properties of the Asbestos Minerals and Biological Behavior 412 Asbestos Fibers in the Lungs of the General Population 414 Fiber Concentration in the Lungs of Occupationally-exposed Groups 416 Effects of Fiber Distribution 421 Effects of Fiber Size 422 Acknowledgments 424 References 424

Chapter 14 B. E. Lehnert

DEFENSE MECHANISMS AGAINST INHALED PARTICLES AND ASSOCIATED PARTICLE-CELL INTERACTIONS

Introduction 427 Deposition of Particles in the Respiratory Tract 427 Particles in the Conducting Airways 431 Local defensive mechanisms against deposited particles 431 Particle-airway epithelial cell interactions 435 Solublization of particles in the conducting airways 437 Kinetics of particle clearance from the conducting airways 437 Particles in the Pulmonary-alveolar Region 439 Defense against particles by alveolar phagocytes 439 Detrimental aspects of the phagocytic protective mechanism 447 Alveolar macrophage-mediated particle clearance 448 Other mechanisms of particle clearance and retention 451 Kinetics of particle clearance from the alveoli 455 Particle "overloading" 456 Acknowledgments 460 References 460

Chapter 15 J. M. G. Davis

IN VIVO ASSAYS TO EVALUATE THE PATHOGENIC EFFECTS OF MINERALS IN RODENTS

Methods of Exposure 471 Pathogenic Potential of Amphiboles and Serpentines 472 Non-pulmonary pathogenesis 474 Importance of fiber geometry 474 Relative pathogenic potential of serpentine and amphibole 475 Pathogenic Potential Man-made Mineral Fibers 476 Pathogenic Potential of Clay Minerals 477 Kaolin minerals 477 Talc 478 Mica 479 Sepiolite and palygorskite ("attapulgite") 479 Vermiculite 480 Pathogenic Potential of Zeolites 480 The Pathogenic Potential of Silica 481 References 483

xiv Chapter 16 K. E. Driscoll

IN VITRO EVALUATION OF MINERAL CYTOTOXICITY AND INFLAMMATORY ACTIVITY

Introduction 489 In Vitro Approaches to Study Mineral Dust Toxicity 490 Cytotoxicity Assays 490 Erythrocyte hemolysis 490 Macrophage toxicity 492 Hemolytic activity and cytotoxicity: Their relationship to in vivo toxicity .495 Macrophage Activation and Inflammatory Activity 496 Active oxygen species 496 In vitro effect of minerals on macrophage cytokine production 500 Summary 504 References 506

Chapter 17 B. T. Mossman

CELLULAR AND MOLECULAR MECHANISMS OF DISEASE

Introduction 513 The Disease Process 513 Carcinogenesis and Fibrosis: General Principles 516 Mechanisms of Lung Cancer by Asbestos and Silica 517 Mechanisms of Mesothelioma by Asbestos 518 Mechanisms of Pulmonary Fibrosis (Asbestosis and Silicosis) 519 Acknowledgments 520 References 520

Chapter 18 U. Saffiotti, L. N. Daniel, Y. Mao, A. O. Williams, M. E. Kaighn, N. Ahmed & A. D. Knapton

BIOLOGICAL STUDIES ON THE CARCINOGENIC MECHANISMS OF QUARTZ

Coordinated In Vivo, Cellular, and Molecular Approaches 523 Crystalline Silica Used by Biological Studies 524 Animal Models and Species Susceptibility 525 Cytokines and gene expression in the pathogenesis of silicosis, alveolar t ype II hyperplasia and lung carcinogenesis 532 Cellular Models for Toxicity and Neoplastic Transformation 536 DNA Binding and DNA Damage by Crystalline Silica 539 Conclusions 541 References 542

xv Chapter 19 V. T. Vu

REGULATORY APPROACHES TO REDUCE HUMAN HEALTH RISKS ASSOCIATED WITH EXPOSURES TO MINERAL FIBERS

Introduction 545 Major Regulations and Guidelines on Asbestos 546 Occupational exposure limits and work practices 546 Air emissions control and waste disposal 547 Control of asbestos exposure in schools and buildings 548 Health standards for drinking water and effluent guidelines 550 Restriction or prohibition of the use of asbestos in certain products and applications 550 Regulatory Activities on Other Mineral Fibers 551 Erionite 551 Refractory ceramic fibers 551 Glass fiber and mineral wool 552 Conclusions 552 References 553

GLOSSARY 555

INDEX 577

xvi