Volatiles in magmas / ed. by M.R.Carroll, J.R.Holloway. - Washington: Mineralogical Society of America, 1994. - xvii, 517 p.: ill. - (Reviews in mineralogy; vol.30). - ISBN 0-939950-36-7; ISSN 0275-0279  Место хранения:   018 | Институт нефтегазовой геологии и геофизики им. А.А.Трофимука | Новосибирск | Библиотека

Оглавление / Contents

Copyright; List of additional volumes of Reviews in Mineralogy ..................................................... ii Foreword ...................................................... iii Editors' Introduction ......................................... iii Dedication to С Wayne Burnham .................................. iv Chronological listing of C. Wayne Burnham's papers ............. iv Chapter 1 VOLCANIC-GAS STUDIES: METHODS, RESULTS, AND APPLICATIONS R.B. Symonds, W.I. Rose, G.J.S. Bluth & Т.М. Gerlach Introduction .................................................... 1 Sampling and In-situ Measurements at High-Temperature Sites ..... 1 Inherent risks and limitations ............................... 1 Health and safety hazards ................................. 1 Sampling bias ............................................. 1 Contamination ............................................. 2 Reactions during cooling .................................. 2 Methods ...................................................... 2 Solution-filled collection bottles ........................ 2 Pre-1975 collection techniques ............................ 4 In-situ gas chromatography ................................ 4 Oxygen fugacity probes .................................... 4 Evaluation of Volcanic-Gas Analyses ............................. 5 General guidelines ........................................... 5 Evaluation procedures ........................................ 5 Air contamination ......................................... 5 Equilibrium-disequilibrium analysis ....................... 6 Common causes of disequilibrium .............................. 6 Oxidation of H2, H2S, or CO ............................... 9 Gains or losses of H2O .................................... 9 Extraneous СН4 and NH3 .................................... 9 Gains of H2 .............................................. 10 Retrieval of equilibrium compositions ....................... 11 Removal of disequilibrium effects ........................ 11 Estimating concentrations of minor and trace species ..... 12 Equilibrium Compositions of High-Temperature Volcanic Gases .... 13 Molecular compositions ...................................... 13 Elemental compositions ...................................... 19 Oxygen fugacities ........................................... 22 Pressure effects ............................................ 23 Shallow Magma Degassing Processes .............................. 24 Degassing at hot-spot and divergent-plate volcanoes ......... 24 Kilauea volcano .......................................... 24 Divergent-plate volcanoes ................................ 26 Generalizations .......................................... 26 Degassing at convergent-plate volcanoes ..................... 26 Showa-Shinzan dome, Japan ................................ 26 Mount St. Helens, U.S.A .................................. 28 White Island, New Zealand ................................ 30 Gas/lava interactions during degassing ...................... 32 Trace-element vapor transport and deposition during degassing ................................................... 34 Remote Sensing of Gas Emissions ................................ 34 Correlation Spectrometer Determination of SO2 .................. 37 Instrumentation and methods .................................... 37 SO2 emissions and volcanic activity ............................ 39 Total Ozone Mapping Spectrometer Determinations of SO2 Emissions ...................................................... 43 Introduction ................................................ 43 Method ...................................................... 43 Basic parameters ......................................... 43 TOMS instruments ......................................... 43 Basic technique .......................................... 44 Limitations .............................................. 44 Sources of error ......................................... 45 Data ........................................................ 46 Applications ................................................ 46 General correlations of SO2 outgassing with eruption characteristics .......................................... 46 Annual SO2 emissions ..................................... 48 Tamden use with COSPEC ................................... 48 Excess S02 from convergent-plate volcanoes .................. 49 Detection of H2S emissions ............................... 51 Emission Rates of Other Volcanic Gases ......................... 51 Methods for measurement ..................................... 51 Methods of estimation ....................................... 53 Measuring both SO2 and CO2 emission rates-an example of the advantages .............................................. 53 Gas Studies to Assess Volcanic Hazards ......................... 54 Direct gas sampling ......................................... 54 Measuring gas emission rates ................................ 56 Continuous monitoring of fumaroles and ambient air .......... 56 Sampling of volcanic crater lakes ........................... 56 An integrated approach to surveillance ...................... 56 Conclusions .................................................... 58 Acknowledgments ................................................ 60 References ..................................................... 60 Chapter 2 Analytical methods for volatiles in Glasses P.D. Ihinger, R.L. Hervig & P.F. McMillan Introduction ................................................... 67 Overview and historical development of analytical techniques .................................................. 67 Bulk extraction techniques ............................... 68 Energetic particle techniques ............................ 70 Vibrational spectroscopic techniques ..................... 71 Raman scattering spectroscopy ............................ 72 Nuclear magnetic resonance ............................... 72 Analytical Methods Involving Bulk Extraction ................... 73 General description of the technique ........................ 73 Application to volatile contents in glasses ................. 76 Hydrogen ................................................. 76 Other volatiles .......................................... 78 Analytical Methods Involving Secondary Ion Mass Spectrometry (SIMS) ......................................................... 78 Introduction ................................................ 78 General description of SIMS techniques ...................... 79 Primary beam characteristics ............................. 79 Secondary ion characteristics ............................ 79 Applications to volatile contents in silicate glasses: Hydrogen .................................................... 81 H analysis using positive secondary ions ................. 81 H analysis using negative secondary ions ................. 84 Hydrogen detection levels ................................ 84 Matrix effects ........................................... 85 Precision ................................................ 86 D/H measurements by SIMS ................................. 86 Applications to volatile contents in silicate glasses: Carbon ...................................................... 86 Carbon detection levels .................................. 86 Precision ................................................ 87 Applications to volatile contents in silicate glasses: Halogens .................................................... 87 Fluorine ................................................. 87 Chlorine ................................................. 88 Sensitivity and precision ................................ 89 Applications to volatile contents in silicate glasses: Sulfur ...................................................... 89 Applications to volatile contents in silicate glasses: Other elements .............................................. 91 Summary of SIMS ............................................. 91 Analytical Methods Involving Vibrational Spectroscopy .......... 91 Introduction ................................................ 91 Vibrational properties of important volatile species ........ 92 OH and H2O ............................................... 92 CO, CO2 and CO32- ......................................... 96 Quantitative vibrational spectroscopy ....................... 99 Infrared absorption: theory .............................. 99 Practical application of the technique .................. 101 Quantitative Raman spectroscopy ......................... 101 References .................................................... 112 Chapter 3 DEVELOPMENT OF THE BURNHAM MODEL FOR PREDICTION OF H2O SOLUBILITY IN MAGMAS C.W. Burnham Historical Perspective ........................................ 123 The Thermodynamic Properties of H2O in Granitic Melts ......... 124 References .................................................... 129 Chapter 4 WATER SOLUBILITY AND SPECIATION MODELS P.F. McMillan Introduction .................................................. 131 Early work: low pressure solubility ........................ 131 The effect of pressure: "square root relationships" ........ 132 Burnham's model for water dissolution ...................... 133 Molecular water as a dissolving species .................... 134 Critical behavior of aluminosilicate-water systems at high pressure and temperature .............................. 137 Microscopic Models for Water Dissolution ...................... 139 SiO2-H20 ................................................... 139 Binary silicate systems .................................... 141 Hydrous aluminosilicate glasses ............................ 143 In-situ Studies at High Temperature and Pressure, and Effects of Relaxation and Proton Exchange ..................... 148 Conclusion .................................................... 152 References .................................................... 152 Chapter 5 Experimental Studies of carbon dioxide in Silicate Melts: Solubility, Speciation, and Stable Carbon isotope behavior J.G. Blank & R.A. Brooker Introduction .................................................. 157 Experimental and Analytical Methods ........................... 158 Experiments ................................................ 158 Analysis ................................................... 159 Solubility Measurements ....................................... 160 Early work ................................................. 160 Selected data .............................................. 160 Pressure dependence ..................................... 160 Temperature dependence .................................. 160 Compositional dependence ................................ 162 The effect of water ..................................... 163 Speciation .................................................... 164 Vibrational spectroscopy ................................... 165 Theory .................................................. 165 Тhе СО2 molecule ........................................ 166 The carbonate molecule .................................. 166 Sample spectra .......................................... 167 The NaA1O2-SiO2 join ................................. 167 Natural melt compositions ............................ 169 NMR spectra ................................................ 170 Dissolution Mechanisms ........................................ 171 Environments of molecular CO2 .............................. 172 Carbonate in NaAlO2-SiO2 compositions ...................... 172 Carbonate in other compositions ............................ 173 Thermodynamic models ....................................... 175 Stable Isotope Fractionation .................................. 176 Introduction ............................................... 176 Experimental fractionation studies ......................... 177 СО2-basalt .............................................. 177 СO2-rhyolite ............................................ 178 Intermediate compositions .................................. 178 Summary ....................................................... 179 Acknowledgments ............................................... 179 Appendix ...................................................... 179 References .................................................... 182 Chapter 6 APPLICATION OF EXPERIMENTAL RESULTS TO C-O-H SPECIES IN NATURAL MELTS J.R. Holloway & J.G. Blank Introduction .................................................. 187 Oxidation State and Fluid Phase Speciation in the C-O-H System at Igneous Temperatures and High Pressures ............. 187 The thermodynamic data ..................................... 188 Fluid speciation calculations .............................. 191 Implications for experiments ............................... 191 Oxidizing conditions: The H2O-CO2 join .................. 191 Reducing conditions: Limits on CO, H2, and CH4 .......... 192 Graphite-Н2О experiments ................................ 191 Practical Calculation of H2O Solubility in Rock Melts ......... 193 The Burnham model .......................................... 194 The Stolper model .......................................... 197 Water-basalt ............................................ 202 Water-rhyolite .......................................... 202 Calculating H20 solubility .............................. 203 CO2 Solubility in Rock Melts .................................. 203 CO2 in basaltic melts ...................................... 203 Rhyolitic melts ............................................ 205 Effects of composition on CO2 solubility in rock melts ..... 207 Calculation of CO2 solubility in rock melts ................ 207 Mixed-Volatile Solubilities in Silicate Melts ................. 208 Water-carbon dioxide mixtures .............................. 208 Degassing at low pressures .............................. 209 CO-CO2 fluids: Carbon species solubility under reducing conditions ................................................. 210 Stable Isotope Partitioning between Volatile Species in Fluid and Melt ................................................ 211 Terminology ................................................ 212 Degassing models ........................................... 213 Experimentally-determined isotopic fractionations and application to natural systems ............................. 215 CO2 ..................................................... 216 H20 ..................................................... 216 Degassing of natural systems ............................ 217 Acknowledgments ............................................... 217 References .................................................... 218 Appendix ...................................................... 221 Spera-Stolper H2O version 1.0 ........................... 221 CO2-H2O Degas version 1.0 ............................... 225 Chapter 7 SOLUBILITIES OF SULFUR, NOBLE GASES, NITROGEN, CHLORINE, AND FLUORINE IN MAGMAS M.R. Carroll & J.D. Webster Introduction .................................................. 231 Sulfur Solubility in Melts .................................... 232 General solubility behavior ................................ 232 Experimental methods of sulfur solubility determination .... 234 Experimental studies at atmospheric pressure ............... 235 High pressure sulfur solubility experiments ................ 240 Sulfur behavior in natural systems ......................... 243 Noble Gas Solubilities in Silicate Melts ...................... 244 Experimental measurements .................................. 244 General solubility behavior ................................ 244 Melt composition and noble gas solubility .................. 244 Alternative treatment of melt composition effects on solubility .............................................. 246 Pressure and temperature dependence of noble gas solubility ................................................. 248 Melt-vapor partitioning of noble gases in natural systems .................................................... 249 Abundance fractionations and magma degassing ............... 251 Nitrogen Solubility in Magmas ................................. 252 Experimental Determination of Halogen Solubilities ............ 252 Analytical techniques for F and Cl ......................... 252 Chlorine solubilities: general approach .................... 254 Chlorine solubilities ...................................... 254 Water- and silica-poor silicate melts ................... 255 Water-poor felsic melts ................................. 255 Cl partitioning between hydrous felsic melts and fluids .................................................. 257 Summary of Cl solubilities .............................. 258 Solubility mechanisms and speciation of Cl in silicate magmas ..................................................... 258 F solubilities: general approach ........................... 259 Water- and silica-poor silicate melts ................... 261 Water-poor felsic melts ................................. 262 Hydrous felsic melts .................................... 262 Summary of F solubilities ............................... 263 Solubility mechanisms and speciation of F in silicate magmas ..................................................... 264 Halogens in Cl- and F-enriched Magmas ......................... 266 Chlorine in magmas ......................................... 267 Fluorine in magmas ......................................... 268 Volcanic degassing of F and Cl ............................. 268 Thermodynamic constraints on Cl and F solubilities ......... 269 Conclusions ................................................... 270 Acknowledgments ............................................... 271 References .................................................... 271 Chapter 8 PRE-ERUPTIVE VOLATILE CONTENTS OF MAGMAS M.С. Johnson, A.T. Anderson, Jr. & M.J. Rutherford Introduction .................................................. 281 Constraints on Pre-Eruptive Volatiles from Natural Glasses .... 282 Constraints on Pre-Eruptive Volatiles from Phase Equilibria ... 284 Volatiles in Basaltic and Andesitic Magmas .................... 287 Volatiles in magmas from Kilauea Volcano, Hawaii ........... 287 H2O in Kilauean magmas .................................. 287 CO2H in Kilauean magmas ................................. 290 Sulfur in Kilauean magmas ............................... 292 Pre-eruptive volatiles in basaltic magmas from other tectonic settings .......................................... 292 Mid-ocean ridge basalts ................................. 292 Arc basalts ............................................. 296 Back-arc basin basalts .................................. 297 Phase equilibria constraints on volatiles in basalts ....... 297 Mineral indicators ...................................... 298 Phase equilibria constraints on volatiles in andesites ..... 300 Volatiles in Dacitic and Rhyolitic Magmas ..................... 302 Rhyolitic glass inclusions ................................. 303 Phase equilibria constraints ............................... 304 Mount St. Helens mafic dacites .......................... 304 Mount Pinatubo dacite ................................... 307 Bishop Tuff rhyolite .................................... 310 Discussion .................................................... 311 Kilauean basaltic magma system ............................. 311 Volatile constraints on high-alumina basalt magma genesis .................................................... 312 Volatile saturation in magmas .............................. 315 Obsidians: the Mono Craters obsidian clasts and domes ...... 317 Volatiles and the oxidation state of magmas ................ 319 Eruption dynamics .......................................... 321 The significance of volatiles in silicic magmas: some speculations ............................................... 321 References .................................................... 323 Chapter 9 THE EFFECT OF H2O, CO2 AND F ON THE DENSITY AND VISCOSITY OF SILICATE MELTS R.A. Lange Introduction .................................................. 331 Silicate Melt Densities ....................................... 332 The effect of temperature, pressure, and composition ....... 332 Composition and temperature at 1 bar .................... 332 Pressure ................................................ 333 The importance of water ................................. 334 Direct P-V-T measurements ............................... 335 Derivation of H2Om from solubility curves ............... 335 What about the speciation of water? ........................ 337 Derivation of H2O,total from solubility curves .............. 337 What value of mH2O,total should be applied to natural liquids? ................................................... 340 Application of magma dynamics .............................. 341 The importance of CO2 ...................................... 341 Derivation of mCO2total from solubility curves .............. 342 What about the speciation of CO2? .......................... 342 The partial molar volume of molecular CO2 in molten albite .................................................. 343 The partial molar volume of dissolved carbonate in molten basalt ........................................... 343 The importance of ƒ°CO2 to derived values of mCO2total ................................................ 343 The effect of CO2 on density of magmatic liquids ........ 344 The effect of F on the density of silicate melts ........ 345 Silicate Melt Viscosities ..................................... 346 Newtonian and non-Newtonian rheology ....................... 347 The effect of composition and temperature at 1 bar ......... 348 Configurational entropy theory of viscosity ................ 350 Natural liquids ......................................... 350 Microscopic mechanisms of viscous flow: NMR constraints .... 353 The effect of pressure on silicate melt viscosity .......... 355 The effect of H2O on silicate melt viscosities ............. 357 The effect of CO2 on silicate melt viscosities ............. 359 The effect of F on silicate melt viscosities ............... 362 Toward a comprehensive model equation for silicate melt viscosity .................................................. 364 Acknowledgments ............................................... 364 References .................................................... 365 Chapter 10 DIFFUSION IN VOLATILE-BEARING MAGMAS E.В. Watson Introduction .................................................. 371 Overview of Basic Diffusion Theory ............................ 371 Nature and theoretical conceptualizations of diffusion ..... 371 Definitions ............................................. 371 Atomistics .............................................. 372 Phenomenology: diffusion equations ...................... 374 Complications ........................................... 375 "Kinds" of diffusion ....................................... 375 Temperature and pressure dependence of diffusion ........... 377 Effect of temperature ................................... 377 Pressure dependence of D ................................ 378 Experimental and Analytical Approaches ........................ 378 General considerations ..................................... 378 The thin-source geometry ................................... 379 Experimental technique .................................. 380 Extraction of diffusivity ............................... 380 The diffusion couple and related approaches ................ 380 Experimental configuration .............................. 380 Extraction of diffusivity ............................... 381 Diffusion in more than one dimension ....................... 382 Diffusion of Dissolved Volatiles in Magmatic Liquids .......... 382 Introduction ............................................... 382 Water and related species .................................. 383 Silicic melt compositions ............................... 383 Basaltic melt ........................................... 389 Carbon dioxide ............................................. 389 Sulfur-related species ..................................... 392 Effect of water ......................................... 394 Role of oxygen fugacity ................................. 394 Halogens ................................................... 395 Fluorine ................................................ 395 Chlorine ................................................ 396 Noble gases ................................................ 398 Effects of Dissolved Volatiles (H2O) on Cation Diffusion ...... 399 Introduction ............................................... 399 Tracer diffusion ........................................... 400 Chemical diffusion ......................................... 403 High field-strength elements ............................ 403 Silica .................................................. 404 Effects of H2O: Recap and final observations ............... 404 Effects of other volatiles: Preliminary information on fluorine and chlorine ...................................... 405 Significance and Applications ................................. 406 Crystal/liquid processes ................................... 406 Growth and dissolution rates ............................ 406 Boundary-layer processes ................................ 407 Bubble growth .............................................. 407 Larger-scale magmatic processes ............................ 408 Acknowledgments ............................................... 409 References .................................................... 409 Chapter 11a PHYSICAL ASPECTS OF MAGMATIC DEGASSING I. EXPERIMENTAL AND THEORETICAL CONSTRAINTS ON VESICULATION R.S.J. Sparks, J. Barclay, С. Jaupart,H.M. Mader & J.C. Phillips Introduction .................................................. 413 Observational Constraints ..................................... 413 Volatile solubility ........................................ 414 Basaltic (low viscosity) systems ........................... 415 Silicic (high viscosity) systems ........................... 415 Viscosity and diffusivity ............................... 416 Eruption styles ......................................... 416 Eruption products ....................................... 418 Bubble Formation .............................................. 420 Nucleation theory .......................................... 420 Experiments on nucleation .................................. 422 Bubble growth .............................................. 424 Diffusive growth ........................................ 424 Decompression of bubbles in high viscosity magma ........ 427 Decompression of high viscosity foams ................... 431 Growth of stretching bubbles ............................ 431 Experimental Degassing ........................................ 432 Conduit Flow Models ........................................... 436 A Conceptual Model for Explosive Volcanism .................... 439 Acknowledgments ............................................... 441 Appendix ...................................................... 441 References .................................................... 443 Chapter l1b PHYSICAL ASPECTS OF MAGMATIC DEGASSING II. CONSTRAINTS ON VESICULATION PROCESSES FROM TEXTURAL STUDIES OF ERUPTIVE PRODUCTS K.V. Cashman & M.T. Mangan Introduction .................................................. 447 Bubble Suspensions and Foams .................................. 448 Nomenclature and structure ................................. 448 Processes that influence structure ......................... 450 Capillary drainage ...................................... 450 Film rupture ............................................ 450 Coalescence ............................................. 451 Ostwald ripening ........................................ 451 Textural Characterization of Pyroclasts ....................... 452 Vesicularity ............................................... 452 Vesicle size, shape and spatial distribution ............... 452 Vesicle shape ........................................... 452 Spatial distribution .................................... 453 Vesicle size and number density ......................... 453 Vesicle size distributions .............................. 454 Vesiculation in Basaltic Systems .............................. 455 Fire fountains ............................................. 455 Tephras ................................................. 456 Effusive eruptions ......................................... 457 Reticulite .............................................. 458 Active lava tubes and surface flows ........................ 459 Solidified lava flows ...................................... 461 Inflated sheet flows .................................... 461 Submarine lava flows ....................................... 463 Vesiculation in Silicic Magmas ................................ 464 Explosive eruptions ........................................ 464 Vesicularity ............................................ 465 Vesicle volume distributions ............................ 466 Vesicle shapes .......................................... 468 Effusive silicic eruptions ................................. 471 Macroscopic textural data ............................... 472 Open-system volatile loss ............................... 473 Conclusions ................................................... 473 Acknowledgments ............................................... 474 References .................................................... 474 Chapter 12 EARTH DEGASSING AND LARGE-SCALE GEOCHEMICAL CYCLING OF VOLATILE ELEMENTS A. Jambon Introduction .................................................. 479 Noble Gases and the Degassing History of the Earth ............ 481 Helium: a non conservative element ......................... 481 Helium in meteorites .................................... 481 The atmospheric budget and helium residence time in the atmosphere .......................................... 482 Cosmogenic helium ....................................... 482 Helium in the ocean: the MORB source and helium flux from the mantle ......................................... 482 The helium :heat-flow relationship ...................... 483 Helium from arc magmas .................................. 484 Helium flux from the continental crust .................. 484 Helium model age of the mantle and outgassing ........... 485 The 3He/4He vs 87Sr/86Sr relationship ..................... 485 Argon and catastrophic versus continuous degassing ......... 487 Argon isotopes in terrestrial reservoirs ................ 487 40Ar and long term terrestrial outgassing ............... 488 Further inferences from Neon and Xenon ..................... 489 Constraints from terrestrial xenology ................... 489 Neon .................................................... 490 CO2 - A Major Volatile with Major Problems .................... 490 The bulk Earth abundance ................................... 491 C/36Ar and bulk Earth carbon ............................ 491 Terrestrial inventory ................................... 492 The C/3He ratio and the flux of CO2 ........................ 495 H2O - A Marginally Volatile Species ........................... 497 Water in the exosphere ..................................... 497 Water in H20:MORB and the H2O:ridge flux ................... 497 Water and subduction ....................................... 498 Sulfur - An Example of Massive Recycling ...................... 499 Long term sulfur cycle ..................................... 499 Sulfur in oceanic basalts .................................. 500 Mantle sulfur ........................................... 502 Halogens ................................................... 502 Fluorine ................................................ 502 Chlorine and bromine .................................... 505 Iodine .................................................. 507 Conclusions ................................................ 508 Acknowledgments ............................................ 509 References ................................................. 509