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WATER in NOMINALLY ANHYDROUS

62 Reviews in and. Geochemistry 62

TABLE OF CONTENTS

1 Analytical Methods for Measuring Water in Nominally Anhydrous Minerals George R. Rossman

INTRODUCTION 1 ANALYTICAL METHODS 2 Early infrared studies 2 Quantitative IR methods 3 specific calibrations 8 Thermogravimetric methods 9

P205 cell coulometry 9 Hydrogen extraction with uranium reduction methods 10 Nuclear methods for hydrogen determination 11 Nuclear magnetic resonance 16 Secondary ion mass spectrometry (SIMS) 18 PREVIOUS REVIEWS OF METHODS 20 SURFACE WATER 21 CURRENT STATUS OF CALIBRATIONS 23 GLASSES 23 ACKNOWLEDGMENTS 24 REFERENCES 24

2 The Structure of Hydrous Species in Nominally Anhydrous Minerals: Information from Polarized IR Spectroscopy Eugen Libowitzky and Anton Beran

INTRODUCTION 29 The importance of hydrous species in NAMs 29 Why use IR spectroscopy? 30 History 30 CONCEPTS OF INFRARED SPECTROSCOPY 31 Introduction to IR spectroscopy 31 Sample requirements 32 ix Water in Nominally Anhydrous Minerals - Table of Contents

Experimental equipment 32 QUANTITATIVE DATA FROM INFRARED SPECTROSCOPY 33 The distance - frequency correlation of hydrogen bonds 33 The spatial orientation of hydrous species 34 Total absorbance: a first step towards quantitative water analysis 35 CONCEPTS OF STRUCTURAL MODELS FROM INFRARED DATA 36 Charge balance and substitution 36 Electrostatic considerations on defect geometry 37 Space requirements: ideal and distorted models 38 Influence on band energies from cation substitution 38 Discrimination among hydrous defects 39 Deuteration 40 I XAMl'l I S 40 Vesuvianite: orientation and hydrogen bonding of hydroxyl groups 40 4 Hydrogarnet substitution - the (OH)4 ~ cluster 41 Water molecules in structural cavities: beryl and cordierite 43 OH substitution in topaz 44 OH incorporation in diopside 44 OH defects in 47 OH traces in corundum 48 ACKNOWLEDGMENTS 49 REFERENCES 49

3 Structural Studies of OH in NominallyAnhydrous Minerals Using NMR Simon C. Kohti

INTRODUCTION 53 PRINCIPLES OF SOI ID STATE NMR 54 Positions of 'H MAS NMR resonances 55 Widths of 'H MAS NMR resonances 55 Intensity of 'H MAS NMR resonances 56 APPLICATION OF II MAS NMR TO NOMINALLY ANHYDROUS MINERALS 58 Attractive features of 'H MAS NMR for studies of NAMs 58 Problems and difficulties in applying 'H MAS NMR to NAMs 58 'H MAS NMR studies of orthopyroxene 59 'H MAS NMR studies of clinopyroxene 60 'H MAS NMR studies of 60 'H MAS NMR studies of garnet 61

'H MAS NMR studies of Si02 polymorphs 61 'H MAS NMR studies of feldspars and other aluminosilicate framework minerals... 61 'H MAS NMR studies of wadsleyite 62 NON-SPINNING II NMR EXPERIMENTS 62 STUDIES OF OTHER NUCLEI IN NAMS 63 PROSPECTS FOR FUTURE DEVELOPMENT OF NMR FOR STUDIES OF NAMS 65 ACKNOWLEDGMENTS 65 REFERENCES 65

x Water in Nominally Anhydrous Minerals - Table of Contents

in Nominally Anhydrous Minerals Kate Wright

INTRODUCTION 67 POINT 1)11 I ( I S IN MINERALS 67 THEORETICAL BACKGROUND 69 Quantum mechanical methods 69 Classical methods 70 Treatment of defects 71 OH DEFECTS IN MANTLE SILICATES 72 The Mg2Si04 polymorphs 73 79 GENERAL REMARKS AND FUTURE DIRECTIONS 80 ACKNOWLEDGMENTS 81 REFERENCES 81

5 Hydrogen in High Pressure Silicate and Oxide Mineral Structures Joseph R. Smyth

INTRODUCTION 85 GEOCHEMISTRY OF H 85 CRYSTAL CHEMISTRY OF H 86 NOMINALLY HYDROUS HIGH-PRESSURE SILICATE PHASES 87 Brucite 90 Serpentine 90 Talc 90 True 91 Chlorite 92 92 Lawsonite 92 Epidote 93 Humite 94 Clinohumite 94 Chondrite 94 Phase A 95 Phase B 96 Superhydrous Phase B 96 Phase D 96 Phase E 97 Phase Pi 97 Topaz-OH 98 Phase Egg 98 K-cymrite 98

xi Water in Nominally Anhydrous Minerals - Table of Contents

NOMINALLY ANHYDROUS HIGH-PRESSURE SILICATE AND OXIDE PHASES 99 Periclase-wiistite 99 Corundum 99 Coesite 101 Stishovite and rutile 101 102 Akimotoite 103 Garnet 104 Olivine 104 Wadsleyite 105 Wadsleyite II 106 106 Anhydrous phase B 107 Kyanite 107 Perovskite 108 Post-perovskite 108 Zircon 109 Titanite 110 CONCLUSIONS 110 ACKNOWLEDGMENT 110 REFERENCES 110

6 Water in Nominally Anhydrous Crustal Minerals: Speciation, Concentration, and Geologic Significance Elizabeth A. Johnson

INTRODUCTION 117 Importance of nominally anhydrous minerals in the crust 117 Scope and goals of this chapter 117 HYDROUS SPECIES AND CONCENTRATIONS IN CRUSTAL MINERALS 118 and coesite 118 Feldspars and nepheline 119 Pyroxenes 122 Garnets 123

Al2Si05 polymorphs 124 Rutile and cassiterite 126 Zircon and titanite 128 Cordierite and beryl 129 UNDERSTANDING GEOLOGIC SYSTI MS 130 Thermodynamic properties 130 Physical properties 134 The water budget of the 136 SUMMARY AND FUTURE POSSIBILITIES 136 ACKNOWLEDGMENTS 137 REFERENCES 137 APPENDIX 142 Studies of hydrogen in quartz 143

xii Water in Nominally Anhydrous Minerals - Table of Contents

Geological studies of H20 and C02 in cordierite 143 Hydrous species in feldspars 144 Structural hydroxyl concentrations in crustal and mantle pyroxenes 146 Structural hydroxyl concentrations in crustal garnets 148 Structural hydroxyl concentrations in kyanite 152 Structural hydroxyl concentrations in sillimanite 152 Structural hydroxyl concentration in andalusite 153 Structural hydroxyl concentrations in rutile 153 Structural hydroxyl concentrations in cassiterite 154

7 Water in Natural Mantle Minerals I: Pyroxenes Henrik Skogby

INTRODUCTION 155 OH ABSORPTION BANDS IN IR SPECTRA 156 Diopside 156 Augite 156 Omphacite 157 Orthopyroxene 157 Absorption from inclusions 158 CORRELATIONS OF OH AND SAMPLE CHEMISTRY 159 WATER CONCENTRATION IN MANTLE PYROXENES 162 IMPLICATIONS FOR WATER IN THE 164 ACKNOWLEDGMENTS 165 REFERENCES 166

8 Water in Natural Mantle Minerals II: Olivine, Garnet and Accessory Minerals Anton Beran and Eugen Libowitzky

INTRODUCTION 169 OLIVINE 170 Basic structure and possible sites of hydrogen incorporation 170 Defect types in mantle-related from different localities 171 Calibration approaches and summary of hydrogen contents 176 GARNET 176 Structural and spectral features 176 Calibration and hydrogen content 180 \( ( I SSORY MINERALS 182 Kyanite 182 Rutile 184 Coesite 185 186 Zircon 186 ACKNOWLEDGMENTS 188 REFERENCES 188 xiii Water in Nominally Anhydrous Minerals - Table of Contents

7 Thermodynamics of Water Solubility and Partitioning Hans Keppler and Nathalie Bolfan-Casanova

INTRODUCTION 193 BASIC THERMODYNAMICS OF WATER SOLUBILITY AND PARTITIONING 194 The meaning of the term "water solubility" 194 Thermodynamics of water solubility 195 Relationship between water solubility and partitioning 198 EXPERIMENTAL STRATEGIES FOR MEASURING WATER SOLUBILITY AND WATER PARTITION ( Oi l 1 l( U N I S 199 Annealing experiments 199 Crystallization experiments 200 WATER IN UPPER MANTLE MINERALS 201 Water solubility in and the A1 content of orthopyroxenes as "geohygrometer" 201 Water solubility in olivine 205 Water solubility in garnet 211 Water solubility in clinopyroxene 211 Water partitioning among upper mantle minerals 212 Water storage capacity of the upper mantle and the origin of the Earth's asthenosphere 214 Water recycling by subducted slabs 215 WATER IN MINERALS 216 Water solubility in wadsleyite and water partitioning between wadsleyite and olivine 216 Partitioning of water between wadsleyite and ringwoodite 219 Partition coefficients of water between other high-pressure phases 220 WATER IN MINERALS OF THE 222 Water in 222 Water in 223 The distribution of water at the 660 km discontinuity 225 THE EQUILIBRIUM DISTRIBUTION OF WATER IN THE EARTH'S INTERIOR 226 ACKNOWLEDGMENTS 227 REFERENCES 227

10 The Partitioning of Water Between Nominally Anhydrous Minerals and Silicate Melts Simon C. Kohn and Kevin J. Grant

INTRODUCTION 231 PARTITIONING OF WATER BETWEEN NAMS AND MELTS; METHODOLOGY AND APPROACH 233 Experimental studies of water partitioning between NAMs and melts 233 SUMMARY, IMPLICATIONS AND FUTURE RESEARCH 238 ACKNOWLEDGMENTS 239 REFERENCES 239

xiv Water in Nominally Anhydrous Minerals - Table of Contents

Daniel J. Frost

INTRODUCTION 243 MANTLE METASOMATISM 244 EVIDENCE 1 ROM MANTLE XI NOI I I IIS 246 Peridotite massifs and xenoliths from alkaline basalts 247 Xenoliths from kimberlites 247 Mantle mineralogy 248 Mantle mineralogy 250 EXPERIMENTAL STUDIES ON THE STABILITY OF KNOWN MANTLE HYDROUS MINERALS 251 Pargasitic amphiboles 251 Apatite 255 Phlogopite 256 K-richterite 259 EXPERIMENTAL STUDIES ON THE STABILITY OF POTENTIAL HIGH PRESSURE HYDROUS MANTLE MINERALS 260 Phase X 261 Humite and dense hydrous magnesium silicate phases 262 THE STABILITY OF HYDROUS PHASES IN ULTRAMAFIC LITHOSPHERE AND THE CONVECTING MANTLE 262 ACKNOWLEDGMENTS 265 REFERENCES 266

1 2 Hydrous Phases and Water Transport in the Subducting Slab Tatsuhiko Kawamoto

INTRODUCTION 273 LOW-PRESSURE HYDROUS MINERALS AND HIGH-PRESSURE HYDROUS PHASES 273 STABILITY OF HYDROUS PHASES IN DOWNGOING PERIDOTITE 277 STABILITY OF HYDROUS PHASES IN DOWNGOING BASALT AND SEDIMENT 279 PRESSURE - TEMPERATURE CONDITIONS AND DEHYDRATION REACTIONS IN THE SUBDUCTING SLAB 280 COMPOSITION AND DIHEDRAL ANGLES OF AQUEOUS FLUIDS IN MANTLE PERIDOTITE 281 SECOND CRITICAL ENDPOINT BETWEEN MAGMAS AND AQUEOUS FLUID: IMPLICATIONS FOR SLAB-DERIVED COMPONENT .282 CONCLUDING REMARKS 285 ACKNOWLEDGMENT 286 REFERENCES 286

xv Water in Nominally Anhydrous Minerals - Table of Contents

I «3 Diffusion of Hydrogen in Minerals Jannick Ingrin and Marc Blanchard

INTRODUCTION 291 BASIC CONCEPTS OF DIFFUSION IN MINERALS 291 EXPERIMENTAL METHODS 292 MEASUREMENT TECHNIQUES 294 Infrared spectroscopy 295 Mass spectrometry 296 Thermogravimetry 297 Nuclear reaction analysis 297 Liquid scintillation counting 298 Proton-proton scattering 298 Theoretical techniques 298 DETECTION OF H DIFFUSION THROUGH ISOTOPE EXCHANGE 299 Anhydrous minerals 299 Hydrous minerals 304 EXTRACTION/INCORPORATION REACTIONS IN ANHYDROUS MINERALS 307 Olivine 307 Diopside 310 313 Garnets 314 Quartz 316 Feldspars 316 CONCLUSION AND FUTURE DIRECTIONS 317 ACKNOWLEDGMENTS 318 REFERENCES 318

14 Effect of Water on the Equation of State of Nominally Anhydrous Minerals Steven D. Jacobsen

INTRODUCTION 321 ELASTIC PROPERTIES OF NOMINALLY ANHYDROUS MINERALS IN THE UPPER MANTLE 322 Olivine 322 Humite-group minerals along the forsterite-brucite join 323 Garnet 323 Grossular-hydrogrossular 326 Pyroxene 326 ELASTIC PROPERTIES OF NOMINALLY ANHYDROUS MINERALS IN THE TRANSITION ZONE 328 Wadsleyite 328 Wadsleyite-II 330 Ringwoodite 330 DENSE HYDROUS MAGNESIUM SILICATES 332 xvi Water in Nominally Anhydrous Minerals - Table of Contents

Phase A 332 Phase-B group minerals 332 Phase D 332 Phase E 334 WATER-ELASTICITY SYSTI M ATK S 334 CALCULATED HYDROUS VELOCITIES IN THE UPPER MANTLE AND TRANSITION ZONE 335 CONCLUSIONS AND FUTURE RESEARCH OPPORTUNITIES 338 ACKNOWLEDGMENTS 338 REFERENCES 338

1 5 Remote Sensing of Hydrogen in Earth's Mantle Shun-ichiro Karato

INTRODUCTION 343 GEOPHYSICAL OBSERVATIONS 344 Electrical conductivity 344 Seismic wave velocities 346 Seismic wave attenuation 346 347 Topography of discontinuity 348 Sharpness of discontinuities 349 PHYSICAL BASIS FOR INFERRING HYDROGEN CONTENT FROM GEOPHYSICAL OBSERVATIONS 349 Electrical conductivity 349 Seismic properties 351 Partial melting? 362 SOME EXAMPLES 363 Water content in the transition zone 363 Distribution of hydrogen in the upper mantle 366 Hydrogen in the lower mantle 369 SUMMARY AND OUTLOOK 370 ACKNOWLEDGMENTS 370 REFERENCES 371

16 The Role of Water in High-Temperature Rock Deformation David L. Kohlstedt

INTRODUCTION 377 BACKGROUND 379 MODELS OF CLIMB-CONTROLLED CREEP 379 THE CASE FOR OLIVINE 381 DISLOCATION CLIMB 383 DIFFUSION 384 DEPENDENCE OF CREEP RATE ON WATER FUGACITY 386

xvii Water in Nominally Anhydrous Minerals - Table of Contents

CONCLUDING REMARKS 388 ACKNOWLEDGMENTS 390 REFERENCES 390 APPENDIX 394 Charge neutrality 394 Flux equations for a semi-conducting silicate 395

1 7 The Effect of Water on Mantle Phase Transitions Eiji Ohtani and K. D. Litasov

INTRODUCTION 397 RECENT PROGRESS ON PRESSURE SCALES FOR THE DETERMINATION OF PHASE BOUNDARIES IN MANTLE MINERALS 398 EFFECT OF WATER ON PHASE TRANSFORMATION 400 Dry and wet phase boundaries in the olivine-wadsleyite transformation 400 Wadsleyite-ringwoodite transformation 401 Post-spinel transformation 401 Post-garnet transformation in basalt (MORB) 404 EFFECT OF WATER ON PHASE TRANSFORMATION KINETICS 406 Olivine-wadsleyite phase transformation kinetics 406 Post-spinel and post garnet phase transformation kinetics 408 IMPLICATION FOR SEISMIC DISCONTINUITIES AND PHASE TRANSFORMATION BOUNDARIES UNDER DRY AND WET CONDITIONS 409 410 km seismic discontinuity and olivine-wadsleyite phase boundary 409 The 660 km seismic discontinuity and the post-spinel transformation: average depth and topography of the 660 km seismic discontinuity 410 The density relation of basalt and peridotite near the 660 km discontinuity 412 Seismic reflectors: the possible existence of fluid in the lower mantle 413 CONCLUDING REMARKS 415 ACKNOWLEDGMENTS 415 REFERENCES 415

18 Water in the Early Earth Bernard Marty and Reika Yokochi

INTRODUCTION 421 ISOTOPIC CONSTRAINTS ON THE ORIGIN OF TERRESTRIAL WATER 422 Hydrogen isotopic ratios 422 Nitrogen and carbon isotopic ratios 424 Noble gas isotopic ratios 424 Other isotopic constraints 427 POTENTIAL WATER CONTRIBUTORS 428 Contribution of water-rich planetary embryos 429 Asteroid contribution 429 Constraints on water delivery by asteroidal material from the terrestrial highly

xviii Water in Nominally Anhydrous Minerals - Table of Contents

siderophile element budget 430 The case of interplanetary dust as a source of terrestrial water 432 PROCESSES OF WATER INCORPORATION IN EARTH 435 Solar nebula 435 Impact degassing 437 Impact erosion 438 Post-accretional role of a proto-atmosphere in the Early Earth's evolution 438 A summary of volatile delivery processes and of their inherent uncertainties 439 Cooling of the primordial Earth 439 I Hi: WATER ( Y( I i: IN I Hi: HADE AN 440 WATER CONTENT OF THE ARCHEAN MANTLE FROM THE COMPOSITION OF KOMATIITES 443 CONCLUSIONS 444 ACKNOWLEDGMENTS 444 REFERENCES 445

1 9 Water and Geodynamics Klaus Regenauer-Lieb

INTRODUCTION 451 WATER IN mi : i rniosi'iii Ri : 452 Water and the rigidity of (oceanic) plates 452 Water and the nucleation of (new) plate boundaries 454 Water and the evolution of plate boundaries 455 Water and the stored energy potential Y 455 Water and the dissipated energy potential ® 457 Solid versus fluid dynamic modeling setups 461 Application to subduction initiation 462 WATER IN IIIi: CONVECTING MANTLE 465 DISCUSSION AND CONCLUSIONS 465 REFERENCES 467 APPENDIX: THERMOMECHANICAL APPROACH 471

Additional Volume Content: COLOR PLATE I 475 COLOR PLATE 2 476 COLOR PLATE 3 477 COLOR PLATE 4 478

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