Sulfur in magmas and melts: its importance for natural and technical processes / ed. by H.Behrens, J.D.Webster. - Chantilly: Mineralogical Society of America; Saint Louis: Geochemical Society, 2011. - xiii, 578 p.: ill., map. - (Reviews in mineralogy and geochemistry; vol.73). - Incl. bibl. ref. - ISBN 978-0-939950-87-4; ISSN 1529-6466  Место хранения:   09 | Институт геохимии им. А.П.Виноградова СО РАН | Иркутск | Библиотека

Оглавление / Contents

1 Studies of Sulfur in Melts - Motivations and Overview Harald Behrens, James D. Webster INTRODUCTION ................................................. 1 Background ................................................ 1 The behavior and importance of sulfur in melts ............ 2 REVIEW CHAPTERS IN THIS VOLUME ............................... 2 REMAINING ISSUES AND CONSIDERATIONS FOR FUTURE RESEARCH ...... 6 ACKNOWLEDGMENTS .............................................. 7 REFERENCES ................................................... 8 2 Analytical Methods for Sulfur Determination in Glasses, Rocks, Minerals and Fluid Inclusions Edward M. Ripley, Chusi Li, Craig H. Moore Erika R. Elswick, J. Barry Maynard, Rick L. Paul Paul Sylvester, Jun Hun Seo, Nobomichi Shimizu INTRODUCTION ................................................. 9 ANALYTICAL TECHNIQUES ....................................... 10 Total sulfur concentration in minerals, rocks and glasses using elemental analyzer - infrared absorption technology ............................................... 10 Total sulfur concentration in minerals, rocks and glasses using elemental analyzer - mass spectrometer technology ............................................... 11 Total sulfur concentration of minerals, rocks and glasses using X-ray fluorescence ......................... 13 "Kiba" method for the determination of sulfur concentration in whole rocks and glasses ................. 15 Nuclear methods (activation analysis) for the determination of sulfur concentration in minerals, rocks and glasses ........................................ 16 Sulfur analysis of minerals and glasses using the electron microprobe ...................................... 19 Analyses of the sulfur concentration of minerals and glasses by secondary ion mass spectrometry (SIMS) ........ 20 Analyses of the sulfur concentration of minerals and glasses by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) ............................ 22 Determination of the sulfur concentration in fluid inclusions by LA-ICP-MS .................................. 31 SUMMARY ..................................................... 32 ACKNOWLEDGMENTS ............................................. 35 REFERENCES .................................................. 35 3 Spectroscopic Studies on Sulfur Speciation in Synthetic and Natural Glasses Max Wilke, Kevin Klimm, Simon C. Kohn INTRODUCTION ................................................ 41 X-RAY EMISSION AND ABSORPTION SPECTROSCOPY .................. 42 S Kα X-ray emission ...................................... 42 Determination of the S oxidation state using EPMA ........ 45 X-ray excited high-resolution X-ray emission spectroscopy ............................................. 46 X-ray absorption spectroscopy ............................ 46 Determination of S oxidation state from XANES ............ 54 Beam damage during Analysis by EPMA and XANES ............ 55 Sulfur redox equilibrium determined in glasses by λ(S Kα) and XANES ........................................ 57 NUCLEAR MAGNETIC RESONANCE .................................. 60 33S NMR of solid model compounds ......................... 61 33S NMR of glasses ....................................... 64 RAMAN AND IR SPECTROSCOPY ................................... 66 Raman spectroscopy of sulfur model compounds ............. 66 Experimental details for Raman spectroscopy on glasses ... 67 Raman spectroscopy on sulfur in glasses .................. 69 Beam damage by Raman Spectroscopy ........................ 71 Determination of the oxidation state using Raman spectroscopy ............................................. 71 SUMMARY AND OUTLOOK ......................................... 72 ACKNOWLEDGEMENTS ............................................ 73 REFERENCES .................................................. 73 4 Diffusion and Redox Reactions of Sulfur in Silicate Melts Harald Behrens, Jan Stelling INTRODUCTION ................................................ 79 SULFUR DIFFUSION STUDIES .................................... 80 Silica glass ............................................. 82 Simple silicate glasses .................................. 82 Borosilicate glasses ..................................... 89 Aluminosilicate melts relevant to magmatic systems ....... 90 COMPARISON TO DIFFUSION OF OTHER VOLATILES .................. 92 EFFECT OF REDOX STATE ON SULFUR DIFFUSION ................... 95 SULFIDE/SULFATE INTERDIFFUSION AND REDOX REACTIONS OF SULFUR ...................................................... 96 Redox reactions in dry melts ............................. 96 Redox reactions in hydrous melts ......................... 98 SULFUR DIFFUSION VERSUS VISCOSITY ........................... 99 SUMMARY AND OUTLOOK ........................................ 102 ACKNOWLEDGMENTS ............................................ 103 REFERENCES ................................................. 103 5 The Role of Sulfur Compounds in Coloring and Melting Kinetics of Industrial Glass Roberto Falcone, Stefano Ceola, Antonio Daneo, Stefano Maurina INTRODUCTION ............................................... 113 SULFUR COMPOUNDS IN INDUSTRIAL GLASS PRODUCTION ............ 114 Sodium sulfate .......................................... 114 Slag .................................................... 114 Glass cullet ............................................ 114 Filter dust ............................................. 114 Pyrite .................................................. 115 Others .................................................. 115 INDUSTRIAL GLASS PRODUCTION ................................ 115 Batch preparation ....................................... 116 Melting ................................................. 117 Batch reactions ......................................... 117 Fining .................................................. 121 Forming and post-forming ................................ 123 OPTICAL PROPERTIES AND COLORS OF INDUSTRIAL SLS CONTAINER GLASS ...................................................... 124 COLOR GENERATION IN SLS GLASSES ............................ 126 SULFUR SOLUBILITY, REDOX AND GLASS COLOR ................... 128 The batch redox number .................................. 129 Experimental melting .................................... 131 CHEMICAL CHARACTERIZATION OF GLASS COLORS .................. 132 BUBBLES IN SLS GLASSES ..................................... 134 Incomplete fining ....................................... 135 Redox ................................................... 135 Reboil .................................................. 135 Deposits ................................................ 136 SUMMARY AND OUTLOOK ........................................ 138 ACKNOWLEDGMENTS ............................................ 138 REFERENCES ................................................. 139 6 О Experimental Studies on Sulfur Solubility in Silicate Melts at Near-Atmospheric Pressure Linda Backnaes, Joachim Deubener INTRODUCTION ............................................... 143 ANALYSIS METHODS FOR SULFUR CONTENT ........................ 144 INDUSTRIAL MELTS ........................................... 144 Effect of oxygen fugacity ............................... 144 Effect of melt temperature .............................. 149 Effect of melt composition .............................. 150 SOLUBILITY OF SULFUR-BEARING WASTE IN MELTS ................ 155 SOLUBILITY OF SULFUR IN NATURAL MELTS AND SYNTHETIC ANALOGS .................................................... 157 SUMMARY AND OUTLOOK ........................................ 160 ACKNOWLEDGMENTS ............................................ 161 REFERENCES ................................................. 161 7 Modeling the Solubility of Sulfur in Magmas: A 50-Year Old Geochemical Challenge Don R. Baker, Roberto Moretti INTRODUCTION ............................................... 167 THERMODYNAMICS AND MODELING SULFUR SOLUBILITY IN MAGMATIC SYSTEMS .................................................... 168 A few necessary definitions and concepts ................ 168 Modeling philosophies ................................... 169 Thermodynamic basis for dissolution of sulfur in silicate melts .......................................... 171 A BRIEF HISTORY OF EXPERIMENTS AND EMPIRICAL MODELS FOR SULFUR SOLUBILITY IN SILICATE MELTS ........................ 175 Sulfur behavior in systems with only sulfur-rich gas and silicate melts at 1 atm ............................. 175 SULFIDE AND SULFATE SATURATION IN SILICATE MELTS ........... 178 Sulfide saturation at 1 bar ............................. 178 Sulfide and sulfate saturation at high-pressure with or without the presence of a hydrous fluid .............. 182 THERMODYNAMIC MODELS FOR THE BEHAVIOR OF SULFUR IN MAGMATIC SYSTEMS ........................................... 191 Sulfur speciation in silicate melts ..................... 192 The thermodynamic model of Moretti and Ottonello ........ 194 GEOLOGICAL APPLICATIONS .................................... 203 CONCLUSIONS ................................................ 208 ACKNOWLEDGMENTS ............................................ 209 REFERENCES ................................................. 209 8 The Sulfur Budget in Magmas: Evidence from Melt Inclusions, Submarine Glasses, and Volcanic Gas Emissions Paul J. Wallace, Marie Edmonds INTRODUCTION ............................................... 215 SULFUR CONCENTRATIONS IN MAGMAS ............................ 216 MAGMATIC DEGASSING OF SULFUR ............................... 221 Degassing and vapor-melt partitioning ................... 221 Degassing inferred from melt inclusions from mafic volcanoes ............................................... 223 Magmatic vapor phase and volcanic gases ................. 226 "Excess sulfur" or more accurately, "excess volatiles" problem ................................................. 229 Magmatic sulfur and ore deposits ........................ 236 Recycling of sulfur in subduction zones ................. 237 ACKNOWLEDGMENTS ............................................ 239 REFERENCES ................................................. 239 9 Distribution of Sulfur Between Melt and Fluid in S-O-H-C-Cl-Bearing Magmatic Systems at Shallow Crustal Pressures and Temperatures James D. Webster, Roman E. Botcharnikov INTRODUCTION ............................................... 247 BACKGROUND ................................................. 249 Experimental background ................................. 250 METHODS .................................................... 251 Experimentation: advantages and challenges .............. 251 Analytical: issues and challenges ....................... 256 EXPERIMENTAL RESULTS ON SULFUR PARTITIONING BETWEEN FLUID AND SILICATE MELT .......................................... 258 Felsic melts - S-H2O±CO2 ................................ 258 Rhyodacitic melts - S-H2O-Cl ............................ 261 Phonolitic melts - S-H2O-Cl ............................. 261 Andesitic melts - S-H2O±CO2+B ........................... 265 Basaltic melts - S-H2O±CO2-Cl ........................... 265 Summary on S partitioning between fluids and rhyolitic to basaltic melts at crustal conditions ................. 269 APPLICATION OF THE EXPERIMENTAL DATA TO PROCESSES OF FLUID EXSOLUTION AND THE EVOLUTION OF MAGMA AND MAGMATIC FLUIDS ..................................................... 271 Magmatic gas composition as an indicator of magma and volcanic degassing activity ............................. 272 Volatile mixing relationships and the influence of S on CO2, H2O, and Cl solubility in melt and new insights on vapor (fluid) saturation infelsic magmas .... 274 SUGGESTIONS FOR FUTURE RESEARCH ............................ 276 ACKNOWLEDGMENTS ............................................ 276 REFERENCES ................................................. 276 10 Sulfur-bearing Magmatic Accessory Minerals Fleurice Parat, François Holtz, Martin J. Streck INTRODUCTION: THE OCCURRENCE OF MAGMATIC SULFUR-BEARING MINERALS ................................................... 285 Magmatic sulfides ....................................... 286 Magmatic sulfates and sulfate-bearing minerals .......... 291 MINERAL STABILITY, PARAGENESES AND MINERAL/MELT PARTITIONING OF SULFUR ..................................... 295 Transition from sulfide to sulfate stability fields in silicate melts .......................................... 295 Stability range of sulfide phases in magmatic systems ... 296 Sulfates and sulfate-bearing minerals ................... 302 THE IMPORTANCE OF S-BEARING ACCESSORY MINERALS FOR DECIPHERING MAGMA RESERVOIR PROCESSES ...................... 306 IN SITU SULFUR ISOTOPE IN S-BEARING MINERALS ............... 308 CONCLUDING REMARKS ......................................... 309 ACKNOWLEDGMENTS ............................................ 309 REFERENCES ................................................. 309 11 Sulfur in Extraterrestrial Bodies and the Deep Earth Denton S. Ebel COSMOCHEMISTRY OF SULFUR ................................... 315 Silicate melts and sulfur in primitive source materials ............................................... 315 Sulfur content of the terrestrial planets ............... 318 EXPERIMENTAL CONSTRAINTS ................................... 318 Element partitioning .................................... 318 Liquid silicate - liquid metal-sulfide .................. 320 Solid metal - liquid metal-sulfide ...................... 321 Sulfide saturation and immiscibility .................... 323 Rheology: wetting and deformation ....................... 324 PLANETARY INTERIORS ........................................ 324 Iron meteorites ......................................... 324 Sulfur in core fractionation ............................ 325 Earth core formation .................................... 326 Sulfur and lithophile element partitioning .............. 328 MAGMAS OF OTHER SOLAR SYSTEM BODIES ........................ 328 CONCLUSIONS ................................................ 330 ACKNOWLEDGMENTS ............................................ 330 REFERENCES ................................................. 330 12 Fining of Glass Melts Hayo Müller-Simon INTRODUCTION ............................................... 337 AGENTS USED FOR CHEMICAL FINING ............................ 339 LABORATORY EXPERIMENTS ON SULFUR CHEMISTRY ................. 341 Equilibrium experiments ................................. 341 Melting experiments ..................................... 344 MONITORING OF THE REACTION PARAMETERS ...................... 348 Oxidation state of iron ................................. 348 Oxygen sensors .......................................... 349 Redox number concepts ................................... 350 Interdependence of redox related measurements ........... 351 MODELS OF INDUSTRIAL SULFUR FINING ......................... 352 Solubility concept ...................................... 352 Equilibrium concepts .................................... 352 Dynamic equilibrium concepts ............................ 353 INVESTIGATIONS UNDER INDUSTRIAL CONDITIONS ................. 355 SUMMARY .................................................... 358 ACKNOWLEDGMENT ............................................. 359 REFERENCES ................................................. 359 13 Sulfur Degassing From Volcanoes: Source Conditions, Surveillance, Plume Chemistry and Earth System Impacts Clive Oppenheimer, Bruno Scaillet, Robert S. Martin INTRODUCTION ............................................... 363 Geodynamics and the geochemical behavior of sulfur ...... 363 Subduction zones ........................................ 364 Ocean ridge environments ................................ 369 Hot spots ............................................... 371 Flood basalts and silicic parts of large igneous provinces ............................................... 372 MEASURING VOLCANIC SULFUR EMISSIONS ........................ 373 Direct sampling ......................................... 377 In situ sensing ......................................... 377 Ultraviolet spectroscopy ................................ 378 Broad-band infrared spectroscopy ........................ 383 Laser spectroscopy ...................................... 385 Satellite remote sensing ................................ 385 INTERPRETATION OF SULFUR-EMISSION DATA ..................... 386 Proportions of sulfur species ........................... 386 Sulfur fluxes ........................................... 387 Sulfur isotopes ......................................... 388 VOLCANIC SULFUR EMISSION TO THE ATMOSPHERE ................. 389 Ice cores ............................................... 392 ATMOSPHERIC AND CLIMATIC IMPACTS OF SULFUR DEGASSING ....... 394 Chemical schemes relevant to volcanic sulfur emissions ............................................... 394 Impacts of tropospheric sulfur emissions from volcanoes ............................................... 398 The atmospheric and climatic impact of the 1991 eruption of Mt. Pinatubo ................................ 399 Requirements for a climate-forcing eruption ............. 404 SUMMARY AND CONCLUSIONS .................................... 405 ACKNOWLEDGMENTS ............................................ 406 REFERENCES ................................................. 406 14 Sulfur Isotopes in Magmatic-Hydrothermal Systems, Melts, and Magmas Luigi Marini, Roberto Moretti, Marina Accornero INTRODUCTION ............................................... 423 BASIC PRINCIPLES ........................................... 424 Terminology of sulfur isotope systematics ............... 424 δ33S and δ36S values .................................... 425 Equilibrium fractionation factors ....................... 426 Isotope geothermometry .................................. 430 SULFUR ISOTOPIC COMPOSITION OF NATURAL SAMPLES ............. 430 Mantle-derived materials and igneous rocks .............. 430 Sulfide and sulfate minerals from magmatic, magmatic-hydrothermal and related ore deposits .......... 431 Sulfur isotopes in magmatic and magmatic-hydrothermal systems ................................................. 434 SULFUR STABLE ISOTOPES AND THE POTENTIAL FOR PROBING DEGASSING AND CRYSTALLIZATION PROCESSES AND SULFUR SOURCES IN MAGMAS .......................................... 452 Magmatic degassing and sulfur isotope fractionation ..... 453 Separation of S-bearing liquids and/or solid phases ..... 454 Parametric assessment ................................... 454 Comparison of analytical S and δ34SΣS data from selected volcanic systems and theoretical models of degassing and separation of sulfides and anhydrite ...... 465 Conclusions and future research ......................... 481 ACKNOWLEDGMENTS ............................................ 482 REFERENCES ................................................. 482 15 Interactions Between Metal and Slag Melts: Steel Desulfurization Jean Lehmann, Michele Nadif INTRODUCTION ............................................... 493 PARTITIONING OF SULFUR BETWEEN SLAG AND METAL MELTS ........ 494 Sulfide capacity ........................................ 494 Modeling ................................................ 495 Desulfurization during secondary metallurgy operations .............................................. 496 METHODS OF DESULFURIZATION ................................. 499 Evolution of S-content during liquid steel refining ..... 499 Desulfurization of steel by steel-slag stirring ......... 501 Slag formers additions .................................. 503 Slag composition ........................................ 503 Stirring conditions ..................................... 503 Desulfurization of steel by lime powder injection ....... 506 SUMMARY AND FUTURE WORK .................................... 507 LIST OF SYMBOLS ............................................ 509 REFERENCES ................................................. 510 16 The Role of Magmatic Sulfur in the Formation of Ore Deposits Adam C. Simon, Edward M. Ripley INTRODUCTION ............................................... 513 GEOCHEMISTRY OF SULFUR IN MAGMATIC-HYDROTHERMAL SYSTEMS .... 514 Sulfur basics ........................................... 514 Behavior of sulfur in silicate melts .................... 516 THE PARTITIONING OF METALS AND SULFUR AMONG MAGMATIC PHASES ..................................................... 519 The partitioning of sulfur between silicate melt and H-O-S-Cl fluid(s) ....................................... 519 Controls on the partitioning of ore metals among silicate melt and crystalline sulfides .................. 519 The partitioning of ore metals among silicate melt, sulfide liquid and sulfide crystals ..................... 523 The partitioning of ore metals among silicate melt and S-bearing aqueous fluid(s) .............................. 527 The transport of ore metals in magmatic-hydrothermal fluid(s) ................................................ 530 The partitioning of ore metals between vapor and brine at temperatures below the water-saturated granite solidus ................................................. 539 PORPHYRY-TYPE ORE DEPOSITS ................................. 540 Porphyry basics ......................................... 540 Tectonic setting and associated magma composition of porphyry deposits ....................................... 540 Source of sulfur in porphyry environments ............... 541 Source of ore fluids in porphyry environments ........... 542 Constraints on the composition of porphyry-ore forming fluids .................................................. 543 Harmonizing fluid transport data from nature and experiments ............................................. 546 Oxidation state of causative magmas: the role of sulfide vs. sulfate ..................................... 546 Causative magma sources: normal or enriched? ............ 549 Deposition of metal-sulfides in the porphyry environment ............................................. 551 Ni-Cu-(PGE) DEPOSITS ....................................... 552 Characteristics and classification of magmatic Cu-Ni-(PGE) deposits .................................... 552 Resource and grade characteristics ...................... 553 A general model for magmatic Ni-Cu ore genesis .......... 554 Source magmas for Ni-Cu deposits ........................ 556 Transport of sulfide melt ............................... 556 PGE DEPOSITS IN LAYERED INTRUSIONS ......................... 557 Characteristics and classification of PGE deposits ...... 557 Models for the genesis of PGE deposits in layered mafic intrusions ........................................ 559 Source magmas for PGE deposits .......................... 563 FUTURE RESEARCH: WHAT DO WE NEED? .......................... 563 ACKNOWLEDGMENTS ............................................ 564 REFERENCES ................................................. 564