EPIDOTES - GBV · REVIEWS IN MINERALOGY AND GEOCHEMISTRY VOLUME 56 2004 EPIDOTES EDITORS: Axel Liebscher GeoForschungsZentrum Potsdam Potsdam, Germany ... IR spectroscopy of monoclinic

REVIEWS IN MINERALOGYAND GEOCHEMISTRY

VOLUME 56 2004

EPIDOTESEDITORS:

Axel Liebscher GeoForschungsZentrum PotsdamPotsdam, Germany

Gerhard Franz Technische Universitdt BerlinBerlin, Germany

FRONT COVER: Photomicrograph of an aggregate of zonedclinozoisite-epidote crystals with 0.40 to 0.56 cations Fe3* per formulaunit from core to rim (crossed polarized light, sample no. 81-370,Min. Collection Techn. Univ. Berlin) from a hydrothermal epidote-quartz vein, Baja California. The picture shows the upper part ofradially grown crystals, which are up to 10 mm long. At the tip theindividual crystal are between = 150 and = 400 um thick. Crystals aremacroscopically pink colored due to a Mn2O3 content of 0.2-0.7 wt%.The outer rim of the crystals as well as crystals grown in an opencrack in the lower part, are macroscopically green epidote with 0.85to 1.04 Fe3* per formula unit, indicating a second growth stage. Thecrystals also show oscillatory zoning (see back cover and chapter 1 byFranz and Liebscher; photos by Irene Preuss; ZELMI at TUB).

Series Editor: Jodi J. Rosso

MINEHALOGICAL SOCIETY OF AMERICAGEOCHEMICAL SOCIETY

SUB Gfittingen 7217 381618

2004 A 21028

TABLE OF CONTENTS

1 Physical and Chemical Properties of the Epidote Minerals-An Introduction-

Gerhard Franz & Axel Liebsche

INTRODUCTIONNOMENCLATURECRYSTAL STRUCTURE

The monoclinic epidote mineralsZoisite (the orthorhombic epidote minerals) 1Monoclinic - orthorhombic structural relationship 1TEM investigations 1

CRYSTAL CHEMISTRY 2<The monoclinic epidote minerals 2<Zoisite (the orthorhombic epidote minerals) 2Microanalysis 2

CHEMICAL ZONING 2iOPTICAL PROPERTIES 2'

Monoclinic epidote minerals 2'Zoisite (the orthorhombic epidote minerals) 3-Gem materials 3<

OCCURRENCE AND PHASE RELATIONS !. '. 3:Al-rich clinozosite and zoisite 3'Fe rich epidote ....: 4(Metasomatism 4Miscibility vs. miscibility gaps 4'.

MORPHOLOGY, TWINNING AND DEFORMATION 1 4'.Morphology, growth and dissolution .' 4'.Twinning 4'Deformation behavior 4'

ACKNOWLEDGMENTS 5REFERENCES 5!APPENDIX A 6(APPENDIX B : 6(APPENDIX C 71APPENDIX D ItAPPENDIX E 7(APPENDIX F 8(

Epidotes- Table of Contents

Mm Thermodynamic Properties ofZoisite, Clinozoisite and Epidote

Matthias Gottschalk

INTRODUCTION 83VOLUME PROPERTIES 85

Volume at reference conditions 85Volume at elevated temperature and pressure 89Coefficient of thermal expansion 89Compressibility 92

THERMAL PROPERTIES 99Heat capacity 99Third law entropy 103Enthalpy of formation 104Third law entropy and enthalpy of formation from databases 106

PHASE EQUILIBRIA 107Pure clinozoisite and zoisite 107Clinozoisite and zoisite solid solutions 109

MIXING PROPERTIES I l lExcess enthalpies for mixing atM3 I l lIdeal mixing atM3 113General comments on results for A/./?

oz0-A//!°czoand.sc'zo--.s

iOczo 114

ORDER-DISORDER 115Nonconvergent ordering attheM3-Ml sites ...._ 115Convergent ordering at the.M3-M3' sites 116

CONCLUSIONS 119ACKNOWLEDGMENTS 121REFERENCES 122

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Spectroscopy of Epidote MineralsAxel Liebsche.

INTRODUCTION 12;ULTRAVIOLET, VISIBLE AND NEAR-INFRARED SPECTROSCOPY 12!

Optical absorption spectra of the monoclinic epidote minerals 12(Optical absorption spectra of the orthorhombic epidote minerals 13<

INFRARED SPECTROSCOPY 13'IR spectroscopy of monoclinic epidote minerals 13!IR spectroscopy of zoisite 14(

MOSSBAUER SPECTROSCOPY 15:Mossbauer spectra of the different epidote minerals 151Intracrystalline Al-Fe3+ partitioning within the Al-Fe3+ solid solution series 16

OTHER SPECTROSCOPIC METHODS 16:X-ray absorption spectroscopy 16:Electron paramagnetic resonance spectroscopy 16'Raman spectroscopy W.Nuclear magnetic resonance spectroscopy 16f

CONCLUDING REMARKS 16fACKNOWLEDGMENTS 16(REFERENCES W,

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Experimental Subsolidus Studieson Epidote Minerals

Stefano Poll & Max W. Schmidt

INTRODUCTION 171THE MODEL SYSTEM CaO-Al2O3-SiO2-H2O (CASH) AND PHASE RELATIONS

INVOLVING ZOISITE 172Zoisite - clinozoisite 172Building the CASH phase diagram on the basis of experimental results 173High pressure stability of zoisite 174High temperature stability of zoisite 176Zoisite vs. lawsonite and fluid-saturation vs. H2O-undersaturation 176

THE JOIN (CLINO-)ZOISITE-EPIDOTE AND THE ROLE OFOXYGEN FUGACITY IN CaO-FeO-Al2O3-SiO2-H2O-O2 (CFASHO) 177

The binary zoisite-epidote Ca2Al3Si3O12(OH)-Ca2Fe3+Al2Si3O12(OH) 177The dependence of epidote-stability on oxygen fugacity 179Fe3+ partitioning between epidote and garnet solid solutions 180

THE SYSTEMS NCASH, CMASH, NCFMASHO AND PHASERELATIONSHIPS IN MAFIC ROCKS 182

Extension of CASH to more complex systems 182The formation of epidote and the greenschist facies 183Greenschist to blueschist transition 184Subdivision of the blueschist facies 185Epidote-eclogites and the pressure stability limit of epidote minerals 185The amphibolite facies ..„ 186Maximizing epidote/zoisite abundance 187

EPIDOTE AND MICAS IN PELITIC AND FELSIC COMPOSITIONS 188EPIDOTE, CARBONATES AND C-O-H FLUIDS 189

Zoisite morphology in experiments on meta-calcsilicates 190OUTLOOK - OPEN TOPICS FOR FUTURE WORK 192ACKNOWLEDGMENTS 192REFERENCES 192

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D Fluid Inclusions in Epidote Mineralsand Fluid Development in Epidote-Bearing Rocks

Reiner Klemd

INTRODUCTION 197MIXED VOLATILE REACTIONS INVOLVING EPIDOTE MINERALS 198

Hydrothermal and low-grade conditions 198Greenschist-facies conditions 198High- and ultra-high pressure metamorphic conditions 200Low-pressure contact metamorphic-metasomatic fluids in skarn deposits 201

FLUID INCLUSION STUDIES: INTRODUCTION OF SOME BASIC CONCEPTS ..203GEOTHERMAL SYSTEMS 206

Introduction 206ACTIVE MAGMATIC HYDROTHERMAL SYSTEMS 207

Los Azufres geothermal fields, Mexico 207Chipilapa geothermal field, El Salvador 208Dixie Valley Geothermal system, Nevada 208Phlegrean geothermal field, Italy 208

FOSSIL SUBMARINE HYDROTHERMAL SYSTEMS 210Ophiolites 210Mid-Atlantic Ridge (MARK area) 212Discussion .'.- 212

LOW-GRADE METAMORPHIC ROCKS 213SKARN DEPOSITS 214

Introduction 214Iron skarn deposits 215Gold skarn deposits '• 216Tungsten skarn deposits :. 217Zinc and tin skarn deposits .' 217Discussion 218

OTHER ORE DEPOSITS 218PLUTONIC ROCKS 219HIGH- AND ULTRA-HIGH PRESSURE (HP AND UHP) METAMORPHISM 219

Introduction 219Tauern Window, Austria 221Munchberg Gneiss Complex, Germany 222Mt. Emilius, Italy 224Dabie-Sulu terrane, China 224Discussion 226

CONCLUDING REMARKS 226ACKNOWLEDGMENTS 227REFERENCES 227

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O Epidote in Geothermal Systems

Dennis K. Bird & Abigail R. Spieler

INTRODUCTION 235MAGMA-HYDROTHERMAL PROCESSES AND EPIDOTE PARAGENESIS 236CIRCUM-PACIFIC MARGIN GEOTHERMAL SYSTEMS 239

Japan 239Philippines 245New Zealand 248Central America 252

MEDITERRANEAN REGION GEOTHERMAL SYSTEMS: LARDERELLO 258GEOTHERMAL SYSTEMS IN RIFTING ENVIRONMENTS 261

Iceland 261Ethiopia 270Salton Trough, California and Baja California 273

FOSSIL HYDROTHERMAL SYSTEMS IN RIFTING ENVIRONMENTS 282Ophiolites 283North Atlantic igneous province 283

CONCLUDING REMARKS 284ACKNOWLEDGMENTS 285REFERENCES 285

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/ Epidote Group Minerals in Low-Medium PressureMetamorphic Terranes

Rodney M. Grapes & Paul W. O. Hoski

INTRODUCTION 30Nomenclature, mineral abbreviations 30

EPIDOTE GROUP MINERALS IN DIFFERENT LITHOLOGIES 30Metabasite 30Quartzofeldspathic rocks 31Calc-silicate rocks 31

Mn, Cr, Sr AND Mg ABUNDANCES OF LOW-MEDIUM PRESSUREMETAMORPHIC EPIDOTE GROUP MINERALS 32

Manganoan epidote 32Chromian epidote 32Strontian epidote 32Mg abundance 32

ROCK OXIDATION INFLUENCE ON EPIDOTE GROUPMINERAL COMPOSITION 32<

COMPOSITION (MISCIBILITY) GAPS BETWEEN EPIDOTE GROUPMINERALS 32'

Clinozoisite-epidote , 32'Zoisite-clinozoisite 33

EPIDOTE GROUP MINERAL FORMING AND CONSUMING REACTIONS INCANMS-H (METABASITE) AND KNCAS-HC,KCMAS-HC (MARL) SYSTEMS 33:

Metabasite j 33:Marl :, •. 33!

RETROGRADE ALTERATION OF ECLOGITE AND BLUESCHISTFACIES ASSEMBLAGES '. 33'

CONCLUSIONS AND OUTLOOK 34(ACKNOWLEDGMENTS 34:REFERENCES 34:

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Epidote Minerals in High P/T Metamorphic Terranes:Subduction Zone and High- to Ultrahigh-Pressure Metamorphism

M. Enami, J.G. Liou & C. G. Mattinson

INTRODUCTION 347Major themes to be addressed 349

EPIDOTE MINERALS IN A TYPICAL BLUESCHIST FACIES METAMORPHISM:THE FRANCISCAN COMPLEX/CALIFORNIA 350

Prograde zoning of Franciscan metabasite in Ward Creek of the Cazadero region ..350Epidote texture and composition 351

EPIDOTE MINERALS IN LAWSONITE BLUESCHIST-ECLOGITE FACIESMETAMORPHISM: PAM-OUEGOA-POUEBO REGION/NEW CALEDONIA 352

Epidote-bearing mineral assemblages 354Compositional range of epidote minerals 355

EPIDOTE MINERALS IN GREENSCHIST/BLUESCHIST-EPIDOTEAMPHIBOLITE-ECLOGITE FACIES METAMORPHISM:THE SANBAGAWA BELT/JAPAN 355

Composition of host rocks and epidote minerals 356Compositional change of epidote minerals with metamorphic grade 361

EPIDOTE MINERALS IN CALCAREOUS MEATASEDIMENTSOF THE ECLOGITE FACIES: EUROPEAN ALPS 364

PARAGENESIS OF EPIDOTE MINERALS IN HP TO UHP ROCKS 365The prograde evolution of HP to UHP rocks 366The peak metamorphism of HP to UHP rocks 368Retrograde stages (stages III and IV) 378

EPIDOTE MINERALS AS AN INDICATOR OF FLUID-ROCK INTERACTIONAND PARTIAL MELTING 379

SOME PECULIAR CRYSTALCHEMICAL ASPECTS OF HP TO UHPEPIDOTE MINERALS 381

Compositional variations within the A(2)-site 381Sector-zoning of epidote minerals 382

LAWSONITE-EPIDOTE RELATIONS 383PARAGENESIS OF EPIDOTE-CLINOZOISITE IN THE

BLUESCHIST-GREENSCHIST TRANSITION 386POTENTIAL OF EPIDOTE MINERALS FOR THERMOBAROMETRY 387EPIDOTE MINERALS AS CARRIERS OF TRACE ELEMENTS DURING

SUBDUCTION 390CONCLUSIONS 391ACKNOWLEDGMENTS 392REFERENCES 393

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Magmatic Epidote

Max W. Schmidt & Stefano P,

INTRODUCTION 3'MAGMATIC EPIDOTE IN INTRUSIVES 4i

Textural evidence for magmatic epidote 4iNatural magmatic epidote - the crowd 4iNatural magmatic epidote-the odd one's 4i

MELTING REACTIONS AND ZOISITE STABILITY AS DEDUCED FROMEXPERIMENTAL STUDIES IN Fe-FREE MODEL SYSTEMS 4l

CaO-Al2O3-SiO2-H2O (CASH) 4iK2O-CaO-Al2O3-SiO2-H2O (KCASH) 41CaO-MgO-Al2O3-SiO2-H2O (CMASH) 41K2O-CaO-MgO-Al2O3-SiO2-H2O(KCMASH) 41

EPIDOTE IN FLUID-SATURATED MAGMAS 41The wet solidus of tonalite and granodiorite 41Epidote-out in tonalite with increasing pressure 4Epidote-out in granodiorite and granite 4Epidote-out in trondhjemite 4Epidote-out in dioritic and gabbroic compositions 4Epidote-out in granites and granitic dikes 4The temperature stability of epidote: the role of anorthite component in magmas... 4How likely is epidote fractionation? 4

THE ROLE OF OXYGEN FUGACITY AND Fe3+ IN CONTROLLINGEPIDOTE IN MAGMATIC SYSTEMS 41

Oxygen fugacity in granitoid bodies : 41Oxygen fugacity, Fe oxidation state and the stability field of magmatic epidote 41

EPIDOTE PHASE RELATIONSHIPS AS A TOOL FOR EXTRACTING !

THE INTRUSION DEPTH 41Discrepancies between estimated intrusion depths and minimum pressure

conditions recorded by epidote-bearing assemblages 41Epidote in the crystallization sequence: a sensitive tool for

estimating pressure conditions 41PHASE RELATIONSHIPS IN H2O-UNDERSATURATED SYSTEMS 47

Epidote in fluid-absent melting processes 47OPEN PROBLEMS 42EPILOGUE 42ACKNOWLEDGMENTS 42REFERENCES 42

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Allanite and Other REE-Rich Epidote-Group Minerals

Reto Giere & Sorena S. Sorensen

INTRODUCTION 431MINERAL CHEMISTRY AND NOMENCLATURE 431

Allanite 432Dissakisite 437Ferriallanite 437Oxyallanite 442Dollaseite 444Khristovite 444Androsite 444

MINOR AND TRACE ELEMENTS IN ALLANITE 446Substitutions in the A sites 446Substitutions in the M sites 449Substitutions in T sites 450Other substitutions 451

RARE EARTH CHARACTERISTICS 452GEOCHRONOLOGY 464RADIATION DAMAGE AND THERMAL ANNEALING 466

Metamict allanite 469Annealing of metamict allanite 470Annealing of fission tracks 472

PHASE RELATIONS 472Allanite in igneous systems '....: 472Allanite in metamorphic*systems 473Allanite in metasomatic systems 478Alteration of allanite 480

OUTLOOK 482ACKNOWLEDGMENTS 483REFERENCES 483

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I I Manganese in Monoclinic Membersof the Epidote Group: Piemontite and Related Minerals

Paola Bonazzi & Silvio Menchei

INTRODUCTION 4SSTRUCTURE AND CRYSTAL CHEMISTRY 4S

M sites 4SA sites 5(T sites 5CHydrogen bonding 5CHigh-temperature behavior 5CUnit-cell parameters 5C

OPTICAL AND SPECTROSCOPIC PROPERTIES 5CCOMPOSITIONAL VARIABILTY OF PIEMONTITE 51OCCURRENCE AND PARAGENESIS OF PIEMONTITE 51

Metamorphic occurrences 51Contact metamorphic and metasomatic occurrences 52Magmatic, pegmatitic, and hydrothermal occurrences 52

PIEMONTITE COMPOSITIONAS A FUNCTION OF P, T AND HOST ROCKCOMPOSITION 52

Sanbagawa belt 52Attic-Cycladic belt '. 52

MONOCLINIC - ORTHORHOMBIC RELATIONS IN MANGANIANEPIDOTE GROUP MINERALS 52

EXPERIMENTAL STUDIES 52CONCLUDING REMARKS :. 53ACKNOWLEDGMENTS : 1 53REFERENCES ; 1 53APPENDIX 54

Table A. Chemical analyses of REE free piemontites from literature 54Table B. Chemical analyses of REE bearing piemontite from literature 55

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Trace Element Geochemistry of Epidote MineralsDirk Frei, Axel Liebscher,

Gerhard Franz & Peter Dulski

INTRODUCTION 553CRYSTAL-CHEMICAL FRAMEWORK FOR THE INCORPORATION OF

TRACE ELEMENTS INTO EPIDOTE MINERALS 554Crystal structure and chemistry of epidote minerals 554Trace element incorporation into A sites 555Trace element incorporation into M sites 557Trace element incorporation into T sites 557

TRACE ELEMENT VARIATIONS IN EPIDOTE MINERALS 558Observed trace element variation 558Large ion lithophile elements (K, Rb, Cs, Sr, Ba, Pb, including Na) 559Actinides 563Rare earth elements and yttrium 563Transition elements (Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn) 567High field strength elements (Zr, Hf, Nb and Ta) 570Other elements 570Anions ; 572

PARTITIONING OF TRACE ELEMENTS BETWEEN EPIDOTE MINERALSAND MELTS, FLUIDS AND OTHER MINERALS 573

Epidote minerals/melt partitioning 573Epidote mineral/hydrous fluid partitioning 576Partitioning between epidote minerals and other minerals 577

CONCLUSIONS AND OUTLOOK .;.. 581Trace element budgets and element recycling 581Survey of epidote minerals provenance 585Open questions 585

ACKNOWLEDGMENTS 585REFERENCES 586APPENDIX A 592APPENDIX B 594APPENDIX C 601APPENDIX D 604

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Stable and Radiogenic Isotope Systematicsin Epidote Group Minerals

Jean Morriso

INTRODUCTION 6CSTABLE ISOTOPE SYSTEMATICS 6C

Experimental studies 6CEmpirical studies involving hydrogen and oxygen isotopes 61

RADIOGENIC ISOTOPE SYSTEMATICS 62SUMMARY 62ACKNOWLEDGMENTS 62REFERENCES 62