Systematics of Fluid Inclusions in Diagenetic Minerals

SEPM Short Course No. 31

SystematicsSystematics ofof FluidFluid InclusionsInclusions inin DiageneticDiagenetic MineralsMinerals

Edited by: Robert Goldstein, James Reynolds

ISBN 1-56575-098-0, CD catalog 61031 Originally published in CD as SEPM Short Course No. 31, ISBN 1-56576-098-0, catalog 60031 Tulsa, Oklahoma, U.S.A., 1994 www.sepm.org

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 SYSTEMATICS OF FLUID INCLUSIONS IN DIAGENETIC MINERALS

SEPM SHORT COURSE 31

ROBERT H. GOLDSTEIN T. JAMES REYNOLDS

SEPM (Society for Sedimentary Geology)

Sedimentary Geology)

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 SYSTEMATICS OF FLUID INCLUSIONS IN DIAGENETIC MINERALS

SEPM SHORT COURSE 31

Robert H. Goldstein T. James Reynolds THE UNIVERSITY OF KANSAS FLUID INC. Department of Geology P.O. BOX 6873 120 Lindley Hall Denver, CO 80206 Lawrence, KS 66045 USA USA

SEPM] SEPM (Society for Sedimentary Geology)

\Sedimentary Cm’logyl

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 ISBN #1-56576-008-5 Additional copies of this publication may be ordered from SEPM. Send your order to SEPM Post Office Box 4756 Tulsa, Oklahoma 74 159-0756 U.S.A.

.. 11

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 CONTENTS

PREFACE ...... xi .. ACKNOWLEDGMENTS...... x11

Chapter 1 INTRODUCTION TO FLUID INCLUSIONS AND THEIR APPLICATIONS

INTRODUCTION ...... 1 Temperature of mineral precipitation ...... 1 Pressure of mineral precipitation ...... 1 Composition and origin of fluids of mineral precipitation ...... 1 Later history of temperature, pressure. and fluid composition ...... 1 Improve understanding of diagenetic systems ...... 2 Improve understanding of subsurface fluid evolution ...... 2 Improve understanding of porosity evolution ...... 2 Improve interpretation of petroleum migration history ...... 2 Improve reconstructions of thermal history ...... 2 Improve reconstructions of tectonic or stratigraphic history ...... 2 HISTORICAL FRAMEWORK ...... 2

Chapter 2 FLUID INCLUSIONS AND THEIR ORIGIN

FLUID INCLUSION APPEARANCE ...... 5 INCLUSION ENTRAPMENT DURING CRYSTAL GROWTH ...... 5 FLUID INCLUSION ENTRAPMENT AFTER CRYSTAL GROWTH ...... 7 FLUID INCLUSION ENTRAPMENT BY MICROFRACTURING DURING CRYSTAL GROWTH .....9 CRITERIA TO DETERMINE ORIGIN OF FLUID INCLUSIONS...... 9 Primary Fluid Inclusions ...... 9 Calcite ...... 9 Dolomite and ankerite ...... 14 Quartz ...... 15 Feldspar ...... 15 Halite ...... 15 Anhydrite ...... 17 ... 111

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 Gypsum ...... 17 Fluorite ...... 18 Secondary and Pseudosecondary Fluid Inclusions ...... 19 SUMMARY ...... 20

Chapter 3 PHASE CHANGES IN FLUID INCLUSIONS: THE BASICS

INTRODUCTION ...... 23 SINGLE COMPONENT SYSTEM H20 ...... 23 Basic Assumptions ...... 23 P-T Conditions of Diagenesis ...... 26 A Fluid Inclusion's Trek Through P-V-T Space...... 26 A Fluid Inclusion's P-V-T Trek in the Laboratory ...... 27 SINGLE COMPONENT SYSTEM CH4 ...... 27 TWO-COMPONENT SYSTEM H2 0-NaC1...... 29 TWO-COMPONENT SYSTEM HZO-CH4 ...... 31 MULTICOMPONENT SYSTEM H2O-PETROLEUM ...... 39 MULTICOMPONENT SYSTEM GAS-PETROLEUM ...... 39 SUMMARY...... 40

Chapter 4 ARE FLUID INCLUSIONS REPRESENTATIVE SAMPLES OF DIAGENETIC FLUIDS?

INTRODUCTION ...... 43 DIAGENETIC FLUID VERSUS INCLUSION FLUID ...... 43 Homogeneous Fluid ...... 43 Heterogeneous Entrapment ...... 44 CHANGES AFTER ENTRAPMENT ...... 44 Reaction With Host Crystal ...... 45 Diffusion Through the Host ...... 46 Change in Volume of the Inclusion Vacuole ...... 46 Change in Shape (Necking Down) ...... 47 Time ...... 47 Size and shape ...... 47 Temperature ...... 47 Fluid composition...... 48 Host composition ...... 48 Strain ...... 48 Effect of necking down ...... 48 Recrystallization of Mineral Host ...... 52 Location in the Crystal...... 53 Deformation ...... 53

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 Irreversible Phase or Chemical Changes After Entrapment ...... 53 Nucleation Metastability ...... 54 Overheating Effects on Density and Composition (Thermal Reequilibration) ...... 55 Assessing the likelihood of reequilibration of an inclusion ...... 59 RETROGRADE FLUID INCLUSION REEQUILIBRATION...... 63 CONCLUSIONS ABOUT REPRESENTATIVENESS OF FLUID INCLUSIONS ...... 63

Chapter 5 THE PHILOSOPHY OF CONDUCTING A FLUID INCLUSION STUDY

INTRODUCTION...... 65 PROCEDURE ...... 65

Chapter 6 FLUID INCLUSION PETROGRAPHY

INTRODUCTION ...... 69 SAMPLING PHILOSOPHY ...... 69 SAMPLE SELECTION CAVEATS ...... 70 PREPARATION OF THICK SECTIONS FOR FLUID INCLUSION ANALYSES ...... 70 Cleavage Fragments ...... 70 Quick Plates ...... 71 Doubly Polished Plates ...... 71 Impregnation ...... 71 Cutting ...... 71 Grinding ...... 71 Polishing ...... 72 Mounting...... 72 Thickness of the plate ...... 72 Polishing machines ...... 73 MICROSCOPE REQUIREMENTS ...... 73 Standard Transmitted Light Petrographic Microscope ...... 73 Fluid Inclusion Microscope ...... 73 Important Microscope Options ...... 74 Trinocular head ...... 74 Incident light fluorescence ...... 74 Closed circuit television (CCTV) ...... 74 Photographic system ...... 75 Spindle stage ...... 75 Image analysis system ...... 75 Crushing stage ...... 75 PETROGRAPHIC ANALYSIS OF FLUID INCLUSIONS ...... 75 Getting Started ...... 76 Determining Inclusion Origin ...... 77

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 Determining Inclusion Composition ...... 77 Determining Ratios of Liquid to Vapor ...... 77 Procedure ...... 78 Determining Pressure ...... 80 Documentation of Petrographic Relationships ...... 80 DETERMINING DIAGENETIC ENVIRONMENTS...... 81 Vadose Zone ...... 81 Low-Temperature Phreatic Zone ...... 83 Elevated Temperature ...... 83 SUMMARY ...... 84

Chapter 7 FLUID INCLUSION MICROTHERMOMETRY

INTRODUCTION...... 87 THE MENTAL PREPARATION ...... 87 SELECTING FIAs FOR MICROTHERMOMETRY ...... 88 SELECTING INCLUSIONS WITHIN FIAs FOR MICROTHERMOMETRY ...... 88 HOW MANY FIAs SHOULD BE MEASURED? ...... 89 RESOLUTION REQUIREMENTS ...... 90 MECHANICAL PREPARATIONS...... 90 Doubly Polished Plates for Microthermometry ...... 90 Microscope Requirements ...... 91 Heating / Cooling Stages ...... 91 PREPARING FOR MICROTHERMOMETRY ...... 92 Size of Sample Used for Microthermometry ...... 93 What to Do First ...... 93 MEASURING HOMOGENIZATION TEMPERATURES ...... 93 MEASURING LOW-TEMPERATURE PHASE CHANGES ...... 95 Determining the Appropriate Chemical System ...... 96 Preparing for freezing ...... 96 Freezing the inclusion ...... 96 First melting, eutectic temperature ...... 98 H20-NaC1model composition ...... 99 H20-NaCl-CaC12 model composition ...... 99 Seawater model composition ...... 101 H20-NaCl-CH4model composition ...... 102 Punting ...... 103 Effect of additional undetected components ...... 103 Low-Temperature Phase Behavior for the H20-NaC1 Model System ...... 103 Recognizing eutectic melting ...... 103 Salinities less than the eutectic composition ...... 104 Cycling technique explained for freezing ...... 105 Freezing m on inclusions lacking bubbles ...... 108 Interpreting Tm ice for H20-NaC1...... 109

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 Higher salinity compositions ...... 110 With final breakdown of hydrohalite ...... 110 Final melting at the eutectic ...... 111 Disappearance of halite daughter crystals ...... 111 Low-Temperature Phase Behavior for the H2O-NaC1-CaCl2 Model System ...... 112 Identifying the system ...... 112 Stable phase equilibria ...... 112 Practical observations ...... 114 Low-Temperature Phase Behavior for the H20-NaC1-CH4Model System ...... 117 H20-dominant inclusions with CH4 ...... 117 Methane-dominant inclusions ...... 119 SUMMARY ...... 121

Chapter 8 DATA PRESENTATION

INTRODUCTION ...... 123 FREQUENCY HISTOGRAMS ...... 123 BIVARIATE PLOTS ...... 125 SUMMARY ...... 125

Chapter 9 PRACTICAL ASPECTS OF GEOTHERMOMETRY

INTRODUCTION...... 127 FIAs WITH CONSISTENT DATA ...... 127 Minimum Entrapment Temperature ...... 128 Entrapment Temperature ...... 128 G as-p o or inclusions ...... 128 Gas-rich inclusions ...... 130 FIAs WITH VARIABLE DATA ...... 132 Highly Variable Liquid-to-Vapor Ratios ...... 134 Moderately Variable Th Data ...... 136 All-liquid inclusions present ...... 136 Convergent trends ...... 137 Petrographic trends ...... 138 Th DATA THAT APPROACH MAXIMUM TEMPERATURE ...... 139 CAN Th's BE HIGHER THAN Tt's? ...... 140 SUMMARY ...... 140

vii

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 Chapter 10 PRACTICAL ASPECTS OF GEOBAROMETRY INTRODUCTION...... 143 MINIMUM PRESSURE OF ENTRAPMENT ...... 143 From Crushing ...... 143 From Determination of the Bubble Point Curve ...... 143 ENTRAPMENT PRESSURE ...... 144 Using a Consistent Fluid Inclusion Assemblage ...... 144 Water-salt system ...... 144 Methane-water-salt system ...... 145 When There is Petrographic Evidence of Immiscibility ...... 145 Low-temperature systems ...... 145 Elevated-temperature systems ...... 146 SUMMARY ...... 146

Chapter 11 CASE HISTORIES INTRODUCTION...... 149 EVALUATING A FLUID INCLUSION STUDY ...... 149 CASE HISTORIES ...... 150 Origin of Late Fracture-Filling Banded Flowstone, Nevada ...... 155 Origin of Calcite Cement in Miocene Strata, SE Spain ...... 156 Origin of Masses of Calcite Spar, Lake Valley Formation, New Mexico ...... 158 Origin of Low-Temperature Plio-Pleistocene Calcite Cement ...... 163 Origin of Pre-Pennsylvanian Calcite, SE Kansas ...... 164 Origin of Carbonate Cement, Plio-Pleistocene Hope Gate Formation, Jamaica...... 165 Origin of Early Calcite Cements, Pennsylvanian of Kansas ...... 167 Fluid Inclusions in Aragonitic Submarine Cement, Belize ...... 168 Origin of Cambrian-Ordovician Calcite Cements, Llano Uplift ...... 168 Origin of Dolomite in Eocene Strata, Enewetak Atoll ...... 170 Oripn of Early Post-Compactional Calcite Cement, Pennsylvanian, Lansing-Kansas City Groups ...... 171 Origin of Mid-Cretaceous Dolomite, Valles Platform, Mexico...... 173 Minimum Temperature of Formation of Halite Associated with Sylvite ...... 175 Calcite Cementation During Progressing Conditions, Permian Laborcita Formation, New Mexico ...... 176 Origin of Calcite and Thermal and Fluid History of Pennsylvanian Holder Formation, New Mexico ...... 177 Origin of Late Post-Compactional Calcite Cement, Pennsylvanian, Lansing-Kansas City Groups ...... 178 Origin of Authigenic Quartz Cement, Upper Jurassic, North Sea ...... 180 Geothermometry and Geobarometry Using Fluid Inclusions in Quartz from the Central Alps ...... 180 SUMMARY ...... 181 ... Vlll

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 Chapter 12 OTHER ANALYTICAL APPROACHES

INTRODUCTION ...... 183 NONDESTRUCTIVE TECHNIQUES ...... 183 Ultraviolet Fluorescence Emission Spectroscopy ...... 183 Infrared Absorption Microspectroscopy ...... 184 Synchrotron X-Ray Fluorescence Microprobe ...... 1~ Laser Raman Microprobe ...... 185 Proton Microprobe ...... 185 Nuclear Magnetic Resonance ...... 185 DESTRUCTIVE TECHNIQUES...... 186 Daughter Minerals ...... 186 EDS of Salts From Fluids in Inclusions ...... 186 Cation and Anion Analyses of Extracted Bulk Samples or of Individual Inclusions ...... 186 Analysis of Solutes Released Directly Into Instrumentation ...... 187 Isotopic Composition of Inclusion Fluids ...... 187 Analyses of Gas Composition ...... 188

REFERENCES CITED ...... 189

ABOUT THE AUTHORS ...... 199

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 PREFACE

The writing of this book evolved from our excitement about the potential uses of the fluid inclusion technique and our dismay over its common misuse in diagenetic minerals. The past decade has revealed significant advantages to using fluid inclusions as a means of understanding the physical and chemical history of fluids in sedimentary basins, but it also has revealed important limitations which have required that a new approach must be employed to effectively use fluid inclusions. Our main stimuli have been interactions with colleagues and students, in which we observed many having great difficulties extracting the basic fluid inclusion methodologies for diagenetic systems from the literature. Many of these people were misapplying fluid inclusions altogether, and had devoted many months of work to produce data of little utility. The end result was significant frustration among many workers and ineffective use of a potentially powerful technique.

In this book we concentrate on teaching the reader what must be known to use fluid inclusion techniques properly for applications in diagenetic minerals. In addition to those working in sedimentary rocks, this text will be useful to workers in other fields: the principles, philosophy, and procedures expressed herein are applicable to any fluid inclusion study, no matter what the emphasis. The text is organized as would be a practical course in the use of fluid inclusions in diagenetic minerals. It is not intended to be a comprehensive encyclopedia of all fluid inclusion work that has been done in sedimentary rocks. The book begins with what fluid inclusions are and what geologic history they are capable of recording. Following are the basic phase equilibria that must be known to understand the behavior of pore fluids and fluid inclusions in nature. Once this is explained, the question of validity of using fluid inclusions as records of ancient diagenetic systems is dealt with in such a way that the questions commonly asked about the limitations of the technique are addressed. These ideas set the stage for showing how to conduct a fluid inclusion study. We set out a new petrographically based approach for conducting fluid inclusion research that is logically followed by methods that allow for the interpretation of compositions of pore fluids that existed in sedimentary rocks, and methods of geothermometry and geobarometry. We then present selected case histories that are designed specifically to give the reader practice in evaluating fluid inclusion data from the diagenetic realm. Finally, we summarize briefly the arsenal of analytical techniques that may be applied to fluid inclusions to develop additional constraints on fluid inclusion composition.

R. H. Goldstein T. J. Reynolds March 1994

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021 ACKNOWLEDGMENTS

The authors wish to thank the many individuals who contributed greatly to the completion of this book. Above all, we wish to thank Christina Baroth and Cindy Keeffe for countless hours of help and moral support. Linda Harris provided clerical help. Careful reviews by J. R. Allan, D. L. Hall, J. J. Irwin and E. Roedder greatly improved the manuscript. R. C. Burruss provided many helpful suggestions and aided in some of the calculations. S. M. Sterner provided samples of synthetic fluid inclusions. Some of the studies summarized in this book were supported by grants from Exxon Production Research, Texaco Research, and BP Research; the University of Kansas general research fund, NSF grants EAR-87-21229, and EAR-92-18463.

xii

Downloaded from http://pubs.geoscienceworld.org/books/book/chapter-pdf/3791478/9781565760981_frontmatter.pdf by guest on 02 October 2021