Carbonates: mineralogy and chemistry / D.J.Barber et al.; ed. by R.J.Reeder. - 2nd printing, with added appendix. - Washington: Mineralogical Society of America, 1990. - xii, 399 p.: ill. - (Reviews in mineralogy; vol.11). - Bibl. ref.: p.395-399. - ISBN 0-939950-15-4; ISSN 0275-0279  Место хранения:   018 | Институт нефтегазовой геологии и геофизики им. А.А.Трофимука | Новосибирск | Библиотека

Оглавление / Contents

COPYRIGHT; LIST OF PUBLICATIONS ................................ ii FOREWORD ...................................................... iii PREFACE; ACKNOWLEDGMENTS ...................................... iii Chapter 1 J. CRYSTAL CHEMISTRY of the RHOMBOHEDRAL CARBONATES Richard J. Reeder INTRODUCTION .................................................... 1 RHOMBOHEDRAL VERSUS HEXAGONAL AXIAL SYSTEMS ..................... 2 THE CO3 GROUP AS A STRUCTURAL UNIT .............................. 4 THE CARBONATES .............................................. 6 The calcite structure ........................................ 6 Calcite isotypes ............................................. 8 Atomic thermal vibrations ................................ 10 Structural variation ..................................... 14 Solid solutions of carbonates ........................... 17 The magnesian calcite solid solution ..................... 17 The CaCO3-CdCO3 solid solution ........................... 20 The Ni-Mg carbonate solid solution ....................... 20 Lattice parameters in other solid solutions ................. 21 THE CARBONATES .............................................. 22 The dolomite structure ...................................... 22 Interatomic distances .................................... 23 Octahedral distortion .................................... 26 Thermal parameters ....................................... 28 Dolomite isotypes ........................................... 28 Ankerite and ferroan dolomite ............................ 28 Kutnahorite .............................................. 31 Other transition metal dolomites ......................... 31 Calcian dolomites and ankerites ............................. 32 Cation order in dolomite-structure carbonates ............... 32 Thermal disordering ...................................... 32 Structural changes ....................................... 35 Disorder in low-temperature dolomites .................... 35 Lattice parameters of dolomite-type carbonates .............. 37 OTHER DOUBLE CARBONATES ........................................ 40 CRYSTAL CHEMISTRY AT HIGH TEMPERATURES AND PRESSURES ........... 43 Thermal expansion ........................................... 43 High-temperature transformations of calcite ................. 45 CaCO3(II) structure ......................................... 45 SUGGESTIONS FOR FUTURE WORK .................................... 46 ACKNOWLEDGMENTS ................................................ 47 Chapter 2 PHASE RELATIONS of RHOMBOHEDRAL CARBONATES Julian R. Goldsmith INTRODUCTION AND EXPERIMENTAL RESULTS .......................... 49 THE END-MEMBER CARBONATES ...................................... 51 DOLOMITE-TYPE COMPOUNDS ........................................ 51 BINARY PHASE RELATIONS ......................................... 51 CaCO3-MgCO3 ................................................. 51 Relations at moderate pressures .......................... 51 Relations at higher pressures and temperatures ........... 55 Additional considerations in subsolidus relations ........ 58 CdCO3-MgCO3 ................................................. 60 CaCO3-MnCO3 ................................................. 60 CaCO3-FeCO3 ................................................. 62 Additional binary joins with a single solvus ................ 63 CaCO3-NiCO3; СаСO3-СоСO3; MgCO3-NiCO3 .................... 63 Binary joins with extensive solid solubility ................ 64 The join CaCO3-ZnCO3 and Zn-dolomite ......................... 64 A note on the asymmetry of the solvi ........................ 65 TERNARY PHASE RELATIONS ........................................ 66 CaCO3-MgCO3-FeCO3 ............................................ 66 CaCO3-MgCO3-MnCO3 ............................................ 70 Order-disorder relations in Fe- and Mn-containing dolomites ................................................... 70 The systems CaCO3-MgCO3-CoCO3 and CaCO3-MgCO3-NiCO3 .......... 72 SUGGESTIONS FOR FUTURE WORK .................................... 75 ACKNOWLEDGMENTS ................................................ 76 Chapter 3 SOLID SOLUTIONS and SOLVI among METAMORPHIC CARBONATES with APPLICATIONS to GEOLOGIC THERMOBAROMETRY Eric 3. Essene INTRODUCTION ................................................... 77 EXPERIMENTAL DATA BASE ......................................... 77 DETERMINATION OF CARBONATE COMPOSITIONS ........................ 78 COMPOSITIONS OF METAMORPHIC CARBONATES ......................... 80 Rhombohedral carbonates ..................................... 81 Orthorhombic carbonates ..................................... 84 SOLVUS LIMITS IN METAMORPHIC CARBONATES ........................ 85 Solvi in the system CaCO3-MgCO3-FeCO3 ....................... 85 Solvi in the system CaCO3-MgCO3-MnCO3 ....................... 86 APPLICATIONS OF CALCITE-DOLOMITE THERMOMETRY ................... 88 Regional metamorphic rocks .................................. 89 Contact metamorphic rocks ................................... 91 THE ARAGONITE-CALCITE TRANSITION AS A THERMOBAROMETER .......... 93 COEXISTING ORTHORHOMBIC AND RHOMBOHEDRAL CARBONATES ............ 94 SUGGESTIONS FOR FURTHER WORK ................................... 95 SUMMARY ........................................................ 95 ACKNOWLEDGMENTS ................................................ 96 Chapter 4 MAGNESIAN CALCITES: LOW-TEMPERATURE OCCURRENCE, SOLUBILITY and SOLID-SOLUTION BEHAVIOR Fred T. Mackenzie, William D. Bischoff, Finley C. Bishop, Michele Loijens, Jane Schoonmaker & Roland Wollast INTRODUCTION ................................................... 97 LOW-TEMPERATURE OCCURRENCE ..................................... 98 Skeletal magnesian calcites ................................. 98 Magnesian calcite cement .................................... 98 UNIT CELL PARAMETERS: BIOGENIC AND SYNTHETIC INORGANIC PHASES ........................................................ 104 High-temperature synthetic materials ....................... 104 Synthesis techniques .................................... 104 Unit cell parameters .................................... 105 Low-temperature synthetic materials ........................ 107 Biogenic materials ......................................... 108 SOLUBILITIES AND SOLID SOLUTION BEHAVIOR ................... 112 Solubilities of magnesian calcites ......................... 114 Dissolution experiments ................................. 114 Precipitation experiments ............................... 118 Interpretation of experimental data ..................... 118 Theoretical considerations ................................. 119 Thermodynamic equilibrium ............................... 120 Stoichiometric saturation ............................... 124 Experimental tests of stoichiometric saturation ......... 126 Expression of solubility ................................ 127 Evaluation of thermodynamic properties from dissolution experiments ................................................ 129 Other approaches to estimation of magnesian calcite properties ................................................. 132 Solid solution properties ............................... 132 Estimation of free energy of mixing from high- temperature data ........................................ 135 Estimation of excess lattice energy .................... 136 Evaluation of the heat of mixing by calorimetric measurements ............................................ 138 Hypothesis of an hydrated magnesian calcite ................ 140 SOME CONCLUDING REMARKS ....................................... 142 ACKNOWLEDGMENTS ............................................... 144 Chapter 5 CRYSTAL CHEMISTRY and PHASE RELATIONS of ORTHORHOMBIC CARBONATES J. Alexander Speer INTRODUCTION .................................................. 145 CRYSTALLOGRAPHY ............................................... 145 Crystal structures ......................................... 145 Charge distribution ........................................ 150 ACO3 polymorphism ......................................... 151 Twinning ................................................... 152 Morphology ................................................. 152 The CaBa(CO3)2 phases ...................................... 154 Carbocernaite .............................................. 157 CHEMISTRY ..................................................... 158 Inorganic orthorhombic carbonates .......................... 158 Biogenic orthorhombic carbonates ........................... 161 Recent shells ........................................... 161 Fossil shells ........................................... 167 IS0T0PIC COMPOSITION .......................................... 169 Dependence on crystal chemistry ............................ 170 Dependence on physical conditions .......................... 170 Dependence on source ....................................... 171 PHASE RELATIONS ............................................... 171 Unary systems .............................................. 171 Binary systems ............................................. 173 CaCO3-SrCO3 ............................................. 173 СаСO3-BаСO3 ............................................. 174 СаCO3-РbCO3 ............................................. 174 SrСO3-ВаСO3 ............................................. 174 SrCO3-PbCO3 ............................................. 175 BaCO3-PbCO3 ............................................. 175 Ternary systems ............................................ 176 Phase relations in aqueous systems ......................... 177 Phase relations involving noncarbonate minerals ............ 178 OCCURRENCE OF ORTHORHOMBIC CARBONATES AND DISCUSSION OF THEIR COMPOSITIONS AND MINERAL ASSEMBLAGES .................... 178 PHYSICAL PROPERTIES ........................................... 182 Density .................................................... 182 Lattice parameters ......................................... 184 Optical properties ......................................... 185 Luminescence ............................................... 188 Magnetic properties ........................................ 188 Infrared and Raman spectra ................................. 188 SUGGESTIONS FOR FUTURE WORK ................................... 189 Chapter 6 POLYMORPHS of CaCO3 and the ARAGONITE-CALCITE TRANSFORMATION William D. Carlson INTRODUCTION .................................................. 191 THE POLYMORPHS OF CALCIUM CARBONATE ........................... 191 The calcite-aragonite equilibrium ......................... 193 CaCO3(II) and CaCO3(III) ................................... 195 CaCO3(IV) and CaCO3(V) ..................................... 196 The role of rotational disorder of CO3 groups .............. 198 Evidence for disordering ................................ 198 Possible disordering schemes ............................ 200 Speculations on disorder in CaCO3 as a function of pressure and temperature ................................ 201 ARAGONITE-CALCITE TRANSFORMATIONS IN THE SOLID STATE ........ 202 The calcite-to-aragonite transformation ................... 202 The transformation under conditions of aragonite stability ............................................... 202 The transformation outside the aragonite stability field ................................................... 203 The aragonite-to-calcite transformation ................... 203 Petrographic observations ............................... 204 Experiments measuring bulk transformation rates ......... 204 Independent determination of growth rates ............... 207 Extraction of nucleation rates from bulk transformation rates .................................... 207 Summary ................................................. 209 THE ARAGONITE-CALCITE TRANSFORMATION IN THE PRESENCE OF WATER ......................................................... 211 Observational evidence for the nature of the aqueous transformation ............................................. 212 Marine environments ..................................... 212 Fresh water environments ................................ 212 Mechanisms of the transformation ......................... 213 Dissolution at surface of parent crystal ................ 214 Nucleation of product crystal ........................... 214 Transport of complexes in solution ...................... 214 Precipitation at surface of product crystal ............. 214 Interpretation of natural occurrences in terms of reaction mechanisms ........................................ 215 Reasons for extremely limited extent of transformation in sea water ............................................ 215 Reasons for apparent differences in transformation type .................................................... 215 Reasons for oriented overgrowths and topotaxial replacement ............................................. 217 Reasons for selective transformation of skeletal materials ............................................... 218 Reasons for long-term preservation in ancient limestone ............................................... 218 Experimental attempts to quantify reaction kinetics ....... 219 The significance of transport processes ................. 219 The time dependence of the overall transformation ....... 219 Inconsistency of a time-squared volume dependence with other observations ...................................... 220 A possible explanation for the time-squared volume dependence .............................................. 222 CONCLUSIONS AND OPPORTUNITIES FOR FURTHER RESEARCH .......... 224 ACKNOWLEDGMENTS ............................................... 225 Chapter 7 The KINETICS of CALCIUM CARBONATE DISSOLUTION and PRECIPITATION John W. Morse INTRODUCTION .................................................. 227 BASIC PRINCIPLES .............................................. 228 REACTION KINETICS IN SIMPLE SOLUTIONS ......................... 231 Dissolution ................................................ 231 General observations .................................... 231 Models and mechanisms ................................... 234 Precipitation .............................................. 238 General observations and models ......................... 238 Secondary nucleation .................................... 239 DISSOLUTION AND PRECIPITATION REACTIONS OF NONBIOGENIC CARBONATES IN COMPLEX SOLUTIONS ............................... 241 General considerations ..................................... 241 Major influences ........................................ 241 Models for reacting surfaces and inhibitors ............. 242 Individual seawater-component influences ................... 244 Magnesium ............................................... 244 Sulphate ................................................ 246 Reaction kinetics in seawater and related solutions ........ 246 Dissolution ............................................. 246 Precipitation ........................................... 247 Other specific influences .................................. 249 Phosphates .............................................. 249 Heavy metals ............................................ 252 Organics ................................................ 253 SPECIFIC TOPICS ............................................. 254 Biogenic carbonate dissolution kinetics .................... 254 General considerations .................................. 254 Influence of grain size ................................. 256 Prediction of solubility from kinetics .................. 258 Kinetic influence on coprecipitation reactions ............. 261 Experimental methods .................................... 261 Cation coprecipitation with calcite ..................... 262 ACKNOWLEDGMENTS ............................................... 264 Chapter 8 TRACE ELEMENTS and ISOTOPES in SEDIMENTARY CARBONATES Ján Veizer INTRODUCTION .................................................. 265 INCORPORATION OF TRACE ELEMENTS INTO CARBONATE MINERALS ....... 267 INCORPORATION OF STABLE ISOTOPES OF OXYGEN AND CARBON INTO CARBONATE MINERALS ............................................ 271 Theoretically predicted composition of carbonate minerals ................................................... 272 Isotopic variations in natural waters ...................... 276 Isotopic composition of natural carbonates ................. 278 INCORPORATION OF RADIOGENIC ISOTOPES INTO CARBONATE MINERALS ...................................................... 279 Radiocarbon ................................................ 279 U-series disequilibrium nuclei ............................. 282 Isotopes of strontium ...................................... 284 DIAGENETIC REPARTITIONING OF TRACERS .......................... 285 RECORD OF TERRESTRIAL EVOLUTION IN ANCIENT CARBONATES ......... 288 Oxygen isotope paleothermometry ............................ 289 Post-Triassic paleoceanography ............................. 289 Carbon isotopes of ancient oceans: the story of life ....... 292 Strontium isotopes and buffering of the oceans ............. 294 Oxygen isotopic composition of sedimentary carbonates ...... 296 Secular variations in chemical composition of carbonates ... 298 CONCLUDING REMARKS ............................................ 299 ACKNOWLEDGMENTS ............................................... 300 Chapter 9 MICROSTRUCTURES in CARBONATES Hans-Rudolf Wenk, David J. Barber & Richard J. Reeder INTRODUCTION .................................................. 301 ORIGINS OF MICROSTRUCTURES .................................... 303 Deformation microstructures ................................ 303 Transformation microstructures ............................. 306 Growth microstructures ..................................... 311 Dislocations ............................................ 311 Growth bands ............................................ 311 Faults .................................................. 313 Stacking disorder ....................................... 313 Twins ................................................... 313 METHODS OF ANALYSIS ........................................... 313 Scanning electron microscopy (SEM) ......................... 314 Transmission electron microscopy (ТЕМ) ..................... 315 Scanning transmission electron microscopy (STEM) ........... 317 High resolution electron microscopy (HREM) ................. 318 POLYMORPHIC TRANSFORMATIONS ................................... 319 Cation ordering in dolomite ................................ 319 Aragonite → calcite transformation ......................... 321 Observations in sedimentary rocks ....................... 322 Observations of the solid state transformation in the ТЕМ ..................................................... 326 VARIATIONS IN STACKING ORDER .................................. 328 Periodic basal superstructure in dolomite .................. 328 Stacking disorder and polytypes in rare earth carbonates ... 329 MODULATED STRUCTURES PARALLEL TO r = {1014} .................. 332 Calcian dolomites .......................................... 332 Saddle dolomites ........................................... 338 Calcite .................................................... 343 Carbonatites ............................................... 344 Interpretation ............................................. 348 OTHER SEDIMENTARY CARBONATES .................................. 352 Recent dolomites ........................................... 352 Magnesian calcites ......................................... 352 DEFORMATION ................................................... 354 Deformation mechanisms ..................................... 354 Calcite ................................................. 355 Dolomite ................................................ 356 The effects of twinning .................................... 357 Biaxiality .............................................. 359 Other defects in deformed carbonates ....................... 359 Dislocations ............................................ 359 Stacking faults ......................................... 360 Stylolites - "Pressure solution" ........................ 364 ACKNOWLEDGMENTS ............................................... 367 REFERENCES .................................................... 369 APPENDIX A partial list of some noteworthy papers that have appeared since the first printing .......................... 395