Holdings: Mineral-water interface geochemistry

Mineral-water interface geochemistry:

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Bibliographic Details
Format:	Book
Language:	English
Published:	Washington, DC Mineralogical Soc. of America 1990
Series:	Reviews in mineralogy 23
Subjects:	Wasser Geochemie Mineralwasser Mineral Aufsatzsammlung
Online Access:	Inhaltsverzeichnis
Physical Description:	XVI, 603 S. zahlr. Ill. u. graph. Darst.
ISBN:	0939950286

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adam_text	TABLE OF CONTENTS Page n Copyright; Additional Copies iii Dedication iv Foreword; Preface and Acknowledgments Chapter 1 M. F. Hochella, Jr. A. F. White MINERAL-WATER INTERFACE GEOCHEMISTRY: AN OVERVIEW 1 INTRODUCTION 3 THE IMPORTANCE OF MINERAL-WATER INTERFACE GEOCHEMISTRY 3 Metals in aquatic systems 4 Ore deposit formation 4 Sorption-concentration of ore metals 6 Hydrothermal leaching as a metal source for ore 6 Low-temperature chemical weathering 9 A Review of This Book 9 Atomistic approaches 10 Adsorption 12 Precipitation and dissolution 13 Oxidation-reduction reactions 15 ACKNOWLEDGMENTS 15 REFERENCES Chapter 2 A. C. Lasaga ATOMIC TREATMENT OF MINERAL-WATER SURFACE REACTIONS 17 INTRODUCTION 23 Definition and measurement of surfaces - crystal habits 26 SURFACE TOPOGRAPHY AND KINETICS 31 REACTION MECHANISMS AND TRANSITION STATE THEORY 36 Application of TST to quartz dissolution 39 AB INJTIO METHODS IN MINERAL SURFACE REACTIONS 39 Ab initio theory 43 Ab initio studies of adsorption 56 Ab initio studies of mechanisms of water-rock kinetics 57 Transition state of the hydrolysis reaction 59 MOLECULAR DYNAMICS METHODS IN SURFACE STUDIES 63 Applications to surfaces 70 MONTE CARLO METHODS IN SURFACE STUDIES 80 REFERENCES Chapter 3 M. F. Hochella, Jr. Atomic structure, microtopography, Composition, and reactivity of mineral surfaces 87 introduction 87 Experimental Techniques 88 Spectroscopies for determining surface composition 88 X-ray photoelectron spectroscopy (XPS) 89 Auger electron spectroscopy (AES) 90 Secondary ion mass spectroscopy (SIMS) 90 Surface analysis by laser ionization (SALI) vi 90 Resonant ionization mass spectroscopy (RIMS) 90 Rutherford backscattering (RBS) 92 Resonant nuclear reaction (RNR) analysis 92 Scanning tunneling spectroscopy (STS) 93 Microscopies for determining surface microtopography 93 Optical methods 94 Scanning electron microscopy (SEM) 94 Transmission electron microscopy (JEM) 94 Scanning tunneling microscopy (STM) 95 Atomic force microscopy (AFM) 95 Tools for determining surface structure 95 Low energy electron diffraction (LEED) 96 Scanning tunneling microscopy (STM) 96 Atomic force microscopy (AFM) 97 Mineral Surface Composition 97 Adventitious modification of mineral surfaces 98 Geochemically modified mineral surface compositions 98 Sorption modification 99 Detachment modification 99 Redox modification 101 Compositional inhomogeneities 103 MINERAL SURFACE MICROTOPOGRAPHY 103 Microtopography models 103 Growth surfaces 105 Cleavage surfaces 105 Dissolution surfaces 108 MINERAL SURFACE ATOMIC STRUCTURE 108 General description of surface atomic structure 108 Surface structures in vacuum 109 Adsorption-induced surface structural modification 109 Structure of various mineral surfaces 111 Galena {001} 111 Hematite {001} 113 Rutile {110} 113 Olivine{010} 113 Albite{010} 116 CalciteflOl} 116 Reactivity of Surfaces 116 Some general concepts concerning surface reaction 116 The two-dimensional phase approximation 117 Heterogeneous (surface) catalysis 117 Examples of the effect of surface microtopography on reactivity 117 Carbon monoxide dissociation on Pt 117 Ethylene decomposition on various metals 119 Adsorption of gases on metals 119 Dissolution of minerals 120 235U sorption on sheet silicates 120 Examples of the effect of surface composition on reactivity 120 Bonding modifiers on the surfaces of catalysts 121 Dissolution rates across the plagioclase series 122 Examples of the effect of surface atomic structure on reactivity 122 Catalytic reactions on single crystal melts 122 Mineral and glass dissolution reactions 123 Sorption reactions on minerals 123 Surface reactivity observed atom by atom 126 CONCLUSIONS 128 ACKNOWLEDGMENTS 128 REFERENCES Chapter 4 G- A- Parks Surface energy and adsorption at mineral/water interfaces: an introduction 133 Introduction 133 particle Size, Shape, and Surface Area 135 thermodynamics 135 Surface free energy 135 Gibbs1 definition of surface excess properties: the dividing surface 137 Contribution of surfaces and interfaces to thermodynamic criteria of equilibrium 137 The Laplace (or Young-Laplace) equation: Curved surfaces imply a pressure gradient 138 The Kelvin effect: Equilibrium constants depend on As 139 The Kelvin equation and vapor pressures 140 The Freundlich-Ostwald equation 141 The Gibbs equation: Adsorption reduces surface free energy 142 REACTIONS WITH WATER 142 Fracture surfaces 142 Hydroxylation 142 High field gradients enhance dissociation of electrolytes 143 Hydration 146 Immersion, surface ionization, and electrified interfaces 147 Surface charge 147 Origins of charge 149 Electrified interfaces 150 SORPTION: REACTIONS WITH AQUEOUS SOLUTES 150 pH and ionic strength dependence 152 Non-specific or physical adsorption 152 Concentration dependence 153 Specific or chemical adsorption 154 Concentration dependence 157 Hydrolysis, polymerization, and precipitation 158 Competition and synergism between adsorbate and complexing ligands 158 Identifying sorption reactions: Clues to the composition and structure of surface complexes 159 Surface charge 162 Proton stoichiometry 162 The last analysis 163 Surface and Interfacial Free Energies of Quartz 163 Fracture surface energy 165 APPLICATIONS 165 Fracture and crack propagation 167 Ostwald ripening and the Ostwald step rule 168 Earthquake prediction 169 ACKNOWLEDGMENTS 169 REFERENCES Chapter 5 J. A. Davis and D. B. Kent surface complexation modeling in aqueous Geochemistry 177 introduction 178 Surface Functional Groups 178 Surface functional groups and mineral types 179 Oxides and aluminosilicates without permanent charge 179 Types of surface hydroxyl groups 179 Density of surface hydroxyl groups 183 Site density determined by adsorption 184 Organic matter 184 Minerals with permanent structural charge 184 Phyllosilicate minerals 185 Kaolinite 185 Smectites, vermiculites, and illitic micas 187 Manganese oxides 187 Carbonate minerals 188 Sulfide minerals 189 Surface area and porosity 189 Physical methods 190 Gas adsorption 190 Adsorption isotherms on minerals 192 BET analysis 192 Problems caused by microporosity 193 Low surface area materials 193 Evaluation of microporosity 195 Surface area of clay minerals and soils 197 ADSORPTION OF IONS AT HYDROUS OXIDE SURFACES IN WATER 197 Adsorption of cations 199 Adsorption of anions 199 Surface site heterogeneity and competitive adsorption of ions 202 Kinetics of sorption reactions 203 Reversibility of sorption processes 204 Effect of solution speciation on ion adsorption 204 Adsorption of hydrophobic molecules 204 the Electrified Mineral-Water Interface 204 Definition of mineral surface charge 205 Classical electrical double layer models 206 The electrical double layer at oxide surfaces 206 The Nernst equation and proton surface charge 209 The zero surface charge condition 211 Zeta potential 212 Early developments of surface coordination theory 213 MODELS FOR ADSORPTION-DESORPTION EQUILIBRIUM 213 Empirical adsorption models 214 Distribution coefficients 214 Langmuir isotherm 215 Freundlich and other isotherms 215 General partitioning equation 217 Surface complexation models 218 Properties of solvent water at the interface 218 Surface acidity of hydrous oxides 219 Surface coordination reactions 219 The Constant Capacitance Model (CCM) 220 The Diffuse Double Layer Model (DDLM) 222 Triple Layer Model (TLM) 225 Four layer models 225 The non-electrostatic surface complexation model 225 Proton stoichiometry in surface complexation reactions 226 Parameter estimation 228 Comparison of the performance of surface complexation models 230 APPLICATIONS IN AQUEOUS GEOCHEMISTRY 231 Surface area and functional groups of soils and sediments 233 Observations of sorption phenomena in complex mineral-water systems 233 Effect of aqueous composition 234 Identification of dominant sorptive mineral components in composite materials 235 Interactive effects of mineral phases 236 Special problems in sorption experiments with natural composite materials 236 The electrical double layer of soils and sediments 237 Use of empirical adsorption models for soils and sediments 237 Distribution coefficients 238 Modeling based on the partitioning equation 239 Use of surface complexation models with soils and sediments 239 Modeling with the non-electrostatic SCM 240 Modeling with electrical double layer corrections 240 SCM modeling to dominant adsorptive components of composite materials 242 Guidelines for surface complexation modeling with natural composite materials 243 CONCLUDING REMARKS 245 ACKNOWLEDGMENTS 245 LIST OF TERMS AND SYMBOLS 246 APPENDIX A. DETAILS OF SURFACE AREA MEASUREMENT 246 Gas adsorption 246 Sample drying 247 t-and as plots 247 Adsorption from solution 248 REFERENCES Chapter 6 G. Spositt MOLECULAR MODELS OF ION ADSORPTION ON MINERAL SURFACES 261 INTRODUCTION 262 Diffuse double Layer Models 262 Modified Gouy-Chapman theory 264 Accuracy of MGC theory 266 Counterion condensation 267 SURFACE COORDINATION MODELS 267 Types of surface coordination 269 The Bragg-Williams approximation 271 Surface complexation equilibria 272 APPLICATIONS 272 Proton adsorption 274 Metal cation adsorption 276 Coion exclusion 278 Concluding remarks 278 acknowledgments 278 references Chapter 7 P. W. Schindlei CO-ADSORPTION OF METAL IONS AND ORGANIC LlGANDS: FORMATION OF TERNARY SURFACE COMPLEXES 281 Introduction 282 Adsorption of organic compounds 282 Hydrophobie expulsion 283 Electrostatic attraction 285 Surface complexation 286 Adsorption of metal ions 286 Electrostatic attraction 287 How to distinguish between inner sphere and outer sphere complexes Co-adsorption of metal ions and organic ligands 288 289 Thermodynamic Stability 289 Conditional and intrinsic constants 291 Evaluating intrinsic stability constants 291 Studies at low surface coverage 291 Extrapolation techniques 292 Double layer techniques 292 Stability constants of ternary surface complexes 292 Definitions 293 Predictions from statistics 296 Experimental results 298 Charge effects 298 Ternary surface complexes with it-acceptor ligands 299 Spectroscopy 299 Methods 300 Results 300 The Role of Ternary surface complexes in nature and Technology 300 Effect of organic ligands upon the fate of trace metals in aquatic environments 302 The structure of the clay-organic interface 304 Ternary surface complexes in froth flotation 304 Ternary surface complexes in heterogeneous redox reactions 305 ACKNOWLEDGMENTS 305 REFERENCES Chapter 8 Gordon E. Brown, Jr. Spectroscopic Studies of Chemisorption reaction mechanisms at oxide-water interfaces 309 INTRODUCTION AND OVERVIEW 310 Chemisorption versus physiosorption 311 The need for molecular-level information about chemisorption reaction mechanisms 313 The structure of clean and real surfaces 319 Overview of Structural Methods Providing Molecular-level information About Chemisorbed Species 320 X-ray absorption spectroscopy (XAS) 324 Production of x-ray absorption spectra 328 XANES andpre-edge spectra 328 EXAFS spectra 329 Analysis of EXAFS spectra 333 Other in situ spectroscopic methods and selected applications 333 Magnetic resonance spectroscopies 335 FTIR and Raman spectroscopy 335 Mössbauer spectroscopy 336 XAS Studies of Chemisorption reaction Mechanisms at Solid/Liquid Interfaces 337 CoOT) on Y-AI2O3 and TiÛ2 (rutile) 341 Co(ü) on kaolinite and a-SiO2 (quartz) 342 Co(II) on calcite 343 Pb(H) on Y-AI2Q3 and a-FeOOH (goethite) 343 Np(V) on a-FeOOH and U(VI) on ferric oxide-hydroxide gels 347 Se oxyanions on a-FeOOH 347 Other XAS studies of sorption complexes at solid/water or solid/air interfaces 348 SEXAFS STUDIES OF MOLECULAR CHEMISORPTION AT SOLID/VACUUM INTERFACES 352 CONCLUSIONS AND OUTLOOK 353 ACKNOWLEDGMENTS 353 REFERENCES Chapter 9 J.-W. Zhang G. H. Nancollas mechanisms of growth and dissolution of Sparingly Soluble Salts 365 INTRODUCTION 365 THE DRIVING FORCES FOR GROWTH AND DISSOLUTION 365 Definition 368 Calculation 369 NUCLEATION 372 THE CRYSTAL-SOLUTION INTERFACE 372 Kink densities 372 Steps from surface nucleation 373 Steps from screw dislocations 375 Crystal Growth rate laws 375 Volume diffusion 375 Adsorption and surface diffusion 376 Integration 377 Surface nucleation 378 Combined mechanisms 379 crystal dissolution rate laws 379 Influence of Additives on the Rates 379 Inhibitory effect of additives 380 Inactivation of kink sites 380 Retardation of step movement 381 Reduction of the concentration of growth units on a terrace 381 Dual effects of additives 382 EXPERIMENTAL METHODS 382 Experimental approaches 382 Free drift method 382 Potenüostaüc method 382 Constant composition method 383 Titrant composition for CC experiments 383 Systems containing only lattice ions 384 Systems involving supporting electrolytes 384 Systems involving acid or base addition 385 Instrumentation for CC method 387 Rate determination 387 EXPERIMENTAL DETERMINATION OF REACTION MECHANISMS 389 GROWTH AND DISSOLUTION OF SOME ALKALINE EARTH SALTS 389 Calcium phosphate 391 Alkaline earth fluoride 392 Calcium carbonate 392 ACKNOWLEDGMENT 393 REFERENCES Xll Chapter 10 W. H. Casey B. Bunker LEACHING OF MINERAL AND GLASS SURFACES DURING DISSOLUTION 397 introduction 398 The Structure of Mdœd-Oxdde Minerals and Glasses 398 The simplified structure of oxide minerals and glasses 399 Reactive and unreactive sites in a structure 404 The effect of temperature 404 GENERAL REACTION MECHANISMS 405 Hydration 407 Ion-exchange reactions 408 Hydrolysis reactions 412 The pH-dependence of leaching rates 414 EXAMPLES 414 Phosphate oxynitride glass 416 Plagioclase 417 Beryl 419 PROPERTIES OF THE LEACHED LAYER 419 Changes in cation coordination with leaching 421 Repolymerization of hydroxyl groups subsequent to leaching 421 Crazing and spallation of the leached layer 423 Chemisorption in the leaching layer 423 CONCLUSIONS 424 ACKNOWLEDGMENTS 424 REFERENCES Chapter 11 J. G. Hering W. Stumm Oxidation and Reductive Dissolution of Minerals 427 INTRODUCTION 428 Objectives 428 BACKGROUND 428 Redox processes in natural systems 428 Major redox couples and the distribution of redox-active species 431 Specific reductants and oxidants 434 Role of the biota 434 Reductive and oxidative dissolution of minerals 434 Some theoretical background 434 Dependence of the rate of surface-controlled mineral dissolution on surface structure 435 Surface-controlled dissolution kinetics and the surface complexation model 437 Reactivity of surface species and redox reactions at mineral surfaces 439 Application of surface complexation model to surface-controlled dissolution: model assumptions 440 Application of the surface complexation model: a generalized rate law for dissolution 440 Application of the surface complexation model: a descriptive example 443 Catalysis of redox reactions by mineral surfaces 445 Case Studies 445 Reductive dissolution of iron oxides 445 Reaction with a reductant 447 Reaction with a reduced metal and a ligand 449 Reaction with a (non-metal) reductant and a ligand 452 Reductive dissolution of manganese oxides 452 Oxidative dissolution of pyrite 453 Oxidative dissolution of uranium(IV) oxides 453 Oxidative dissolution of iron (H) silicates 454 Discussion 454 Applicability and limitations of the surface complexation model 454 Laboratory studies 454 Applicability to field observations 455 Dissolution and its reverse: precipitation 456 Some geochemical implications 458 concluding remarks 459 acknowledgments 459 References Chapter 12 A. F. White HETEROGENEOUS ELECTROCHEMICAL REACTIONS ASSOCIATED WITH OXIDATION OF FERROUS OXIDE AND SILICATE SURFACES 467 Introduction 469 Solid state electrochemistry 471 oxidation of Ferrous-Containing Oxides 472 Solid state electron transfer 472 Solid state oxidation 473 Oxide electrode processes 480 Heterogeneous redox reactions 480 Reductive dissolution involving transition metals 482 Oxidative electron transfer 483 Oxidation of Ferrous Ortho- and Chain silicates 484 Solid state electron transfer 485 Solid state oxidation 487 Dissolution processes 487 Coupled electron-cation transport 489 Dissolved oxygen reduction 491 Actinide reduction on olivine and basalt 491 Nitrate reduction 493 Oxidation of Micas 494 Oxidation of structural Fe 495 Dissolution 496 Heterogeneous redox reactions 498 Reduction of transition metals 498 Reduction oforganics 500 Oxidation of Clay Minerals 500 Structural oxidation 501 Dissolution 501 Heterogeneous reduction reactions 501 Reduction of transition metals 503 CONCLUSIONS 505 ACKNOWLEDGMENTS 505 REFERENCES XIV Chapter 13 G. M. Bancroft M. M. Hyland Spectroscopic Studies of adsorption/Reduction reactions of aqueous metal complexes on Sulphide Surfaces 511 INTRODUCTION 513 BRIEF REVIEW OF LABORATORY STUDIES 514 SURFACE STUDIES OF METAL COMPLEX/SULPHIDE SYSTEMS 514 An introduction to X-ray photoelectron spectroscopy (XPS) 520 An introduction to Auger electron spectroscopy (AES) and a comparison of techniques 522 The chemistry of the surface from XPS and Raman spectroscopies 535 Spatial distribution of metal species from SEM and Auger studies 542 Other techniques for obtaining surface information 546 Summary of mechanisms 552 GEOCHEMICAL IMPLICATIONS OF THE LABORATORY STUDIES 552 The nature of Au in natural sulphides from SEM, SIMS, and Mössbauer studies 555 ACKNOWLEDGMENTS 555 REFERENCES Chapter 14 T. D. Waite Photo-redox Processes at the Mineral-Water Interface 559 INTRODUCTION 560 PHOTO-REDOX PROCESSES INVOLVING ABSORPTION BY MINERALS 560 Electronic structure and optical properties of minerals 560 Molecular orbital theory 563 Band theory 566 Semiconducting minerals 568 Effects of illumination 568 Charge carrier mobility 569 Interfacial electron transfer 569 Surface states 571 Space charge layer, band bending and electron transfer 576 Factors influencing semiconductor reactivity 576 Morphology 577 Size 579 Substitutional doping 579 Surface modification 580 Attachment to supports 580 Intercalation of foreign species into semiconductors 581 Applications of geochemical significance 581 Photodissolution of semiconducting minerals 584 Hydrogen peroxide production 586 Degradation of organic and inorganic pollutants 587 photo-redox processes involving interfacial charge transfer to the Mineral Substrate 587 Charge injection into semiconductors 588 Charge transfer via adsorbed chromophores 589 Charge transfer via photoactive surface complexes XV 590 PHOTO-REDOX PROCESSES INVOLVING CHROMOPHORES ADSORBED ON OR INCORPORATED IN MINERAL SUBSTRATES 591 Photoprocesses of chromophores adsorbed to silica and clay surfaces 591 Photoprocesses on paniculate silica and silica gel 593 Photoprocesses on clay minerals 593 Photoprocesses in zeolites 593 General features of zeolites 594 Photochemistry of inorganic ions exchanged into zeolites 595 Photochemistry of organic molecules in zeolites 595 CONCLUSIONS 597 REFERENCES XVÏ
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series	Reviews in mineralogy
series2	Reviews in mineralogy
spelling	Mineral-water interface geochemistry M. F. Hochella ... eds. Mineral water interface geochemistry Washington, DC Mineralogical Soc. of America 1990 XVI, 603 S. zahlr. Ill. u. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Reviews in mineralogy 23 Wasser (DE-588)4064689-0 gnd rswk-swf Geochemie (DE-588)4020198-3 gnd rswk-swf Mineralwasser (DE-588)4114605-0 gnd rswk-swf Mineral (DE-588)4074836-4 gnd rswk-swf (DE-588)4143413-4 Aufsatzsammlung gnd-content Mineral (DE-588)4074836-4 s Wasser (DE-588)4064689-0 s Geochemie (DE-588)4020198-3 s DE-604 Mineralwasser (DE-588)4114605-0 s Hochella, Michael F. Sonstige oth Reviews in mineralogy 23 (DE-604)BV000002349 23 HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=002629346&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis
spellingShingle	Mineral-water interface geochemistry Reviews in mineralogy Wasser (DE-588)4064689-0 gnd Geochemie (DE-588)4020198-3 gnd Mineralwasser (DE-588)4114605-0 gnd Mineral (DE-588)4074836-4 gnd
subject_GND	(DE-588)4064689-0 (DE-588)4020198-3 (DE-588)4114605-0 (DE-588)4074836-4 (DE-588)4143413-4
title	Mineral-water interface geochemistry
title_alt	Mineral water interface geochemistry
title_auth	Mineral-water interface geochemistry
title_exact_search	Mineral-water interface geochemistry
title_full	Mineral-water interface geochemistry M. F. Hochella ... eds.
title_fullStr	Mineral-water interface geochemistry M. F. Hochella ... eds.
title_full_unstemmed	Mineral-water interface geochemistry M. F. Hochella ... eds.
title_short	Mineral-water interface geochemistry
title_sort	mineral water interface geochemistry
topic	Wasser (DE-588)4064689-0 gnd Geochemie (DE-588)4020198-3 gnd Mineralwasser (DE-588)4114605-0 gnd Mineral (DE-588)4074836-4 gnd
topic_facet	Wasser Geochemie Mineralwasser Mineral Aufsatzsammlung
url	http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=002629346&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA
volume_link	(DE-604)BV000002349
work_keys_str_mv	AT hochellamichaelf mineralwaterinterfacegeochemistry

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