Oxide Minerals-Petrologic and Magnetic Significance

523 Pages·1991·285.069 MB·English

by  Donald H Lindsley, Ed.

REVIEWS in MINERALOGY Volume 25
OXIDE MINERALS:
PETROLOGIC AND
MAGNETIC SIGNIFICANCE
DONALD H. LINDSLEY, EDITOR
The authors:
Subir Banerjee J. Nell
Dept. of Geology & Geophysics Dept. of Geological Sciences
University of Minnesota Bristol University
Minneapolis, Minnesota 55455 Queen's Road
Bristol BS8 lRJ England
Benjamin P. Burton
National Institute of Standards and Richard O. Sack
Technology, B150/223, Div. 450 Dept. of Earth &
Gaithersburg, Maryland 20899 Atmospheric Sciences
Purdue University
B. Ronald Frost E. Lafayette, Indiana 47907
Dept. of Geology &Geophysics
University of Wyoming Glenn A. Waychunas
Laramie, Wyoming 82071 Center for Materials Research
Stanford University
Mark S. Ghiorso Stanford, California 94305
Dept. of Geological Sciences
Bernard J. Wood
Universi ty of Washington
Seattle, Washington 98195 Dept. of Geological Sciences
Bristol University
Stephen E. Haggerty Queen's Road
Bristol BS8 lRJ England
Dept. of Geology &Geography
University of Massachusetts
Amherst, Massachusetts 01003 A. B. Woodland
Bayerisches Geoinstitut
Donald H. Lindsley Bayreuth
Dept. of Earth &Space Sciences Federal Republic of Germany
State University of New York
Stony Brook, New York 11794
Series Editor:
PAUL H. RIBBE
DEPARTMENT OFGEOLOGICAL SCIENCES
Virginia Polytechnic Institute and State University
Blacksburg, Virginia 24061
COPYRIGHT: 1991
MINERALOGICAL SOCIETY of AMERICA
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REVIEWS in MINERALOGY
Formerly: SHORT COURSE NOTES
ISSN 0275-0279
Volume 2S
OXIDE MINERALS: THEIR PETROLOGIC
ANDMAGNETIC SIGNIFICANCE
ISBN 0-939950-30-8
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Vol. Year Pages Editor(s) Ii!k
1974 284 P. H. Ribbe SULFIDEMINERALOGY
2 1983 362 P. H. Ribbe FELDSPARMINERALOGY(2nd edition)
3 out of print OxIDEMINERALs
4 1977 232 F. A. Mumpton MINERALOGy ANDGEOLOGYOFNATURALZEoUfES
5 1982 450 P. H. Ribbe oaraosnrccrss (2nd edition)
6 1979 380 R.G.Bums MARINEMINERALs
7 1980 525 C. T. Prewitt PYRoXENEs
8 1981 398 A. C. Lasaga KINETIcsOFGEOCHEMICALPROCEssES
R. J. Kirkpatrick
9A 1981 372 D. R. Veblen AMPHIBOLESANDOrnER HYDROUSPYRmOLES-
MINERALOGY
9B 1982 390 D. R. Veblen AMPHIBOLES:PETROLOGYANDExPERIMENTAL
P. H. Ribbe PHAsERElATIONS
10 1982 397 1.M. Ferry C!!ARACfERlZATIONOFMETAMORPlllSMTIIROUGH
MINERALEQUILIBRIA
II 1983 394 R. J. Reeder CARBONATES:MINERALOGy ANDCHEMISTRY
12 1983 644 E.Roedder FLUIDINCLUSIONS(Monograph)
13 1984 584 S. W. Bailey MICAS
14 1985 428 S. W. Kieffer MICROSCOPICTOMACROSCOPIC:ATOMIC
A. Navrotsky ENvIRONMENTSTOMINERALTllERMODYNAMICS
15 1990 406 M. B. Boisen, Jr. MATIIEMATICALCRYSTALI1lGRAPHY(Revised)
G. V. Gibbs
16 1986 570 J. W. Valley STAELEISOTOPESINHIGHTEMPERATURE
H. P. Taylor, Jr. GEOLOGICALPROCESSES
J. R. O'Neil
17 1987 500 H. P. Eugster TllERMODYNAMICMODEUlNGOFGEOLOGICAL
I.S. E. Carmichael MATERIALS: MINERALS.FLUIDS.MELTS
18 1988 698 F. C. Hawthorne SPECTROSCOPICMETHODSINMINERALOGy AND
GEOLOGY
19 1988 698 S. W. Bailey HYDROUSPHYLLOslllCATES(EXCLUSIVEOFMICAS)
20 1989 369 D. L. Bish MODERNPOWDERDIFFRACTION
J. E. Post
21 1989 348 B. R. Lipin GEOCHEMISTRYANDMINERALOGYOFRAREEARTH
G. A. McKay ELEMENTS
22 1990 406 D. M. Kerrick THEA12SiOSPOLYMORPHS(Monograph)
23 1990 603 M. F. Hochella, Jr. MINERAL-WATERINTERFACEGEOCHEMISTRY
A. F. White
24 1990 314 J. Nicholls MODERNMETHODSOFIGNEOUSPETROLOGY-
J. K. Russell UNDERSTANDINGMAGMATICPROCESSES
DEDICATION
In the years since the last Oxides Volume appeared (1976), two giants in
oxide mineralogy have passed away: Paul Ramdohr, the consummate ore mineralo-
gist whose ability to identify and interpret silicate minerals in reflected light was
also truly astounding, and Arthur F. Buddington, an eminent silicate petrologist who
came to cherish "opaques" only late in his career, but whose impact on the under-
standing of Fe-Ti oxide minerals was enormous.
We dedicate this book with great respect and affection to the memory ofthose
pioneers of oxide mineralogy, A. F. Buddington and Paul Ramdohr.
The Photograph
In 1962 Iwas a young postdoctoral fellow at the Geophysical Laboratory stu-
dying Fe-Ti oxides experimentally. I had started out accepting the gospel that there
was extensive solubility of ilmenite in magnetite -the assumption underlying the 1955
magnetite-ilmenite thermometer of Buddington, Fahey, and Vlisidis. A few workers
like Knut Heier and E. A Vincent, however, were promoting the heresy (first pro-
mulgated by V. M. Goldschmidt even before ulvospinel had been found in nature or
synthesized in the laboratory), that the classic trellis "exsolution" texture of ilmenite
lamellae in the (111) planes of magnetite might actually result from the oxidation of
FeTi0 component in the magnetite. It turned out to be remarkably easy for me
2 4
to produce that trellis texture by controlled oxidation of ulvospinel-rich solid solu-
tions under hydrothermal conditions at 1-2 kbar and 600-1000"C. One of the best
examples resulted from oxidizing pure FeTi0 at l()()()OC and 670 bar for 1.5hours,
2 4
with the oxygen fugacity imposed by the walls of the stellite pressure vessel (approx-
imately NNO). Paul Ramdohr was visiting the Geophysical Laboratory at the time
and very kindly took a photograph of it (facing page).
Meanwhile, Buddington had written anew manuscript on oxide thermometry,
and had sent it to me for comments. Two things were very clear: the manuscript was
fatally flawed by the assumption of extensive FeTi0 solubility in magnetite, and I
3
in tum needed Bud's vast array of analytical data in order to apply the new
magnetite-ilmenite thermometer/oxybarometer that was emerging from my experi-
ments. I suggested to Bud that we combine forces -all he had to do was to forswear
exsolution and accept the radical notion that ilmenomagnetites formed byoxidation!
Bud was already in his seventies, and it would have been understandable had he
refused. But he was A F. Buddington, and he wrote back, "Sure - if you can con-
vince me of the oxidation hypothesis." I sent him the photograph, and he responded,
"You win; let's write the paper."
It is poignantly ironic that Ramdohr, whose then state-of-the-art photograph
made the Buddington-Lindsley collaboration possible, never accepted the importance
in nature of the oxidation process for producing the trellis ilmenomagnetite texture.
I cherish a reprint of a paper that the Professor, then past 90, wrote defending the
exsolution origin of ilmenomagnetite. On the cover he inscribed "Dr. Lindsley mit
bestem Gruss. Was sagen Siejetzt [What do you have to say now]? Paul Ramdohr".
May we all be so active and feisty in our nineties!
D. H.Lindsley
v
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OXIDE MINERALS: PETROLOGIC
AND MAGNETIC SIGNIFICANCE
FOREWORD
The Mineralogical Society ofAmerica has been publishing Reviews inMineral-
ogysince 1974. See opposite page for a list of available volumes. This is the first of
25 volumes that has been redone and expanded under a new title and volume num-
ber. "Oxide Minerals: Their Petrologic and Magnetic Significance" was edited by
Don Lindsley and represents contributions of 11authors.
As editor of Reviews, I thank Don Lindsley for a great job of pressuring
authors and helping with final copy editing - far above the call of duty. Marianne
Stem did most of the paste-up for camera-ready copy. Her tireless efforts with a
tedious job are greatly appreciated.
Paul H. Ribbe
Blacksburg, VA
April 2, 1991
EDITOR'S IN1RODUCTION
This volume is scheduled to be published in time to be used as the textbook
for the Short Course on Fe-Ti Oxides: Their Petrologic and Magnetic Significance,
to be held May 24-27, 1991, organized by B.R. Frost, D.H. Lindsley, and S.K
Banerjee and jointly sponsored by the Mineralogical Society of America and the
American Geophysical Union.
It has been fourteen and a half years since the last MSA Short Course on
Oxide Minerals and the appearance of Volume 3 of Reviews in Mineralogy. Much
progress has been made in the interim. This is particularly evident in the coverage
of the thermodynamic properties of oxide minerals: nothing in Volume 3, while in
contrast, Volume 25 has three chapters (6, 7,and 8) presenting various aspects ofthe
thermodynamics of oxide minerals; and other chapters (9, 11, 12) build extensively
on thermodynamic models. The coverage of magnetic properties has also been con-
siderably expanded (Chapters 4, 8, and 14). Finally, the interaction of oxides and
silicates is emphasized in Chapters 9, 11, 12, 13,and 14. One of the prime benefits
ofReviews inMineralogy has been that any scientist can afford to have it at his or her
fingertips, Because Volume 3 is out of print and will not be readily available to
newcomers to our science, as much as possible we have tried to make Volume 25 a
replacement for, rather than a supplement to, the earlier volume. Chapters on crys-
tal chemistry, phase equilibria, and oxide minerals in both igneous and metamorphic
rocks have been rewritten or extensively revised. The well received photographs of
oxide textures in Volume 3 have been collected and expanded into a "Mini-Atlas" In
Volume 25. Topics that receive less attention than in the earlier volume are oxides
in lunar rocks and meteorites, and the manganese minerals. We hope that the new
volume will tum out to be as useful as the previous one was.
iii
Thisvolume hasbeen made possible bythe efforts ofmanypeople. The au-
thors have produced manuscripts ofhigh quality. However, it isSeries Editor Paul
Ribbe and hisstaffwhohave converted those manuscripts,in lessthan twomonths,
into the finished volume, and the authors join me in offering a heartfelt thanks to
them for this remarkable achievement.
Donald H. Lindsley
StonyBrook, N. Y.
April 2, 1991
10 microns
iv
TABLE OF CONTENTS
Page
ii Copyright; Additional volumes ofReviews inMineralogy
iii Foreword and Editor's Introduction
iv Dedication
Chapter 1
B. Ronald Frost
INTRODUCTION TO OXYGEN FUGACITY
AND ITS PETROLOGIC IMPORTANCE
1 THE IMPORTANCEOFOXYGENFuGACITY
3 CALmRATIONOFOXYGENFuGACITY
4 ANOVERVIEW OFOXYGENFuGACITY SPACE
6 SOME COMMON MISCONCEPTIONS
6 Buffers
7 Oxygen asfluid species
8 Ferrous/ferric ratio
8 REFERENCES
Chapter 2
Glenn A. Waychunas
CRYSTAL CHEMISTRY OF
OXIDES AND OXYHYDROXIDES
11 INTRODUCTION
11 What iscrystalchemistry?
12 Solid solubility
14 Order-disorder
14 Element sitepartitioning
14 Electronic properties peculiar tooxides
15 DEFECTS ANDNONSTOICHIOMETRY
16 BASIC STRUCTURAL TOPOLOGIES
16 HCP and CCP 0 and OH arrangements
18 NaCI structure
18 Perovskite structure
18 Fluorite andrutile structures
18 Spinel structure
22 Rhombohedral oxide structures
22 IRONOXIDES
22 Wtistite, magnesiowtistite and other solid solutions
23 Hematite, hydrohematite andprotohematite
24 SPINELS
24 Predictions anddeterminations ofcation sitepreference in spinels
25 Magnetite, ulvospinel andtitanomagnetites
30 Maghemite, titanomaghemite
32 Distorted spinel-likephases
33 IRONOXYHYDROXIDES
33 Goethite
34 Akaganeite
34 Lepidocrocite
37 Feroxyhyte
37 Ferrihydrite andprotoferrihydrite
vii
38 TITANIUM AND IRON- TITANIUM OXIDES
40 Rutile
40 Pseudorutile
40 Anatase
42 Brookite
43 Ilmenite, solid solutions andrelated phases
43 Pseudobrookite solid solutions
46 MANGANESE OXIDES AND OXYHYDROXIDES
47 Tetraavalent manganese oxides andoxyhydroxides
47 Pyrolusite
47 Rarnsdellite
47 Nsutite
47 Hollandite andrelated phases
51 Romanechite
51 Todorokite
52 LAYER STRUCTIJRE MANGANESE OXYHYDROXIDES (PHYLLOMANGANA TES)
52 Chalcophanite
53 Birnessite
54 Buserite
54 Asbolane
54 Vemadite
55 Lithiophorite
55 TR!V ALENT MANGANESE OXIDES AND OXYHYDROXIDES
55 Bixbyite
55 Groutite andfeitknechtite
55 Manganosite
56 ALUMINUM OXIDES AND OXYHYDROXIDES
56 Corundum
56 Boehmite anddiaspore
56 COMPLEX OXIDE GROUPS
56 Pyrochlore group
58 Columbite-tantalite group
59 OTHER SIGNIFICANT OXIDES
59 Perovskites
59 Uraninite
61 BIBLIOGRAPHY AND REFERENCES
Chapter 3 Donald H. Lindsley
EXPERIMENT AL STUDIES OF OXIDE MINERALS
69 INTRODUCTION
69 Synthesis vs.phase equilibrium
70 Control ofexperimental conditions
70 Oxygenfugacity
70 Containerproblem
71 Minerals andphases considered
72 Fe-Ojoin
72 Witstite
72 Thermodynamically impossible diagramfor wiistite
73 Effects of highpressures onwustite
73 Magnetite
73 FeZ03 inmagnetite
73 Hematite
74 Melting ofironoxides inthepresence ofC-O vapor
74 Ti02
viii
74 FeO-Ti02 join
79 Fe20:3-Ti02 join
79 FeO-Fe203-Ti02(-Ti203) join
79 Magnetite-ulvospinel joln
79 Hematite-ilmenitejoin
80 Pseudobrookite- ''ferropseudobrookite'' join
80 13000Cisotherm
86 Phaserelationsat othertemperatures
87 Titanomaghemites .
87 Reduction ofFe-Ti oxides
87 Fe-O-MgO-Ti02 SYSTEM
87 FeO-MgO join
87 FeO-MgO-Fe20:3 join
88 FeO-MgO-Ti02-(Ti203) join
90 FeO-Fe20:3-MgO-Ti02 join
90 Fe-O-MnO- Ti02 SYSTEM
90 FeO-Fe203-MnO join
92 Mn-O-Ti02 join
93 FeO-MnO-Ti02 join
93 FeO-Fe20:3-MnO-Ti02 join
94 Fe-O-A1203-Ti02 AND Fe-O-MgO-A1203 SYSTEMS
94 Fe203-A120:3 join
95 FeO-Fe20:3-Al20:3join
95 MgO-Al203join
95 FeO-MgO-Fe203-AI203 systems
95 FeO-Al20:3-Ti02 join
98 FeO-Fe203-A120:3 systems
98 Cr203-BEARING SYSTEMS
98 FeCr204-Fe304-FeAI204 join
98 MISCELLANEOUSSYSTEMS
100 ACKNOWLEDGMENTS
100 REFERENCES
Chapter 4 Subir K. Banerjee
MAGNETIC PROPERTIES OF FE- TI OXIDES
107 INTRODUCTION
107 CRYSTALSTRUCTIJREAND COMPOSITION
109 Rhombohedral oxides
110 Spinel oxides
III Cation-deficient spinel
113 INTRODUCTIONTOTHEORIESOFMAGNETICSUPEREXCHANGE
114 Antiferromagnetism
114 Ferrimagnetism
117 Non-collinear structures
117 SATURATIONMAGNETIZATIONAND CURIE (AND NEEL)POINTS
119 Rhombohedral oxides
120 Spinel oxides
121 Cation-deficient spinels
122 MAGNETOCRYSTALLINEANISOTROPYAND MAGNETOSTRICTION
122 Basic theory
123 Isotropic points
126 OVERVIEWAND CONCLUSION
127 ACKNOWLEDGMENTS
127 REFERENCES
IX
Chapter 5 Stephen E. Haggerty
OXIDE TEXTURES - A MINI-ATLAS
129 INTRODUCTION
130 Mini-Atlas
130 OXIDATIONOFFe-Ti SPINELSANDILMENITES
130 Oxidation oftitanomagnetite
131 Trellis types
132 Sandwich types
132 Composite types
132 Oxidation ofttianomagnetite-tlmeniie intergrowths
135 Oxidation ofdiscreteprimary ilmenite
137 REFERENCES
Chapter 6 M. S. Ghiorso & R. O. Sack
THERMOCHEMISTRY OF THE OXIDE MINERALS
221 INTRODUCTION
221 CRYSTAL CHEMICAL CONSTRAINTSONTHERMODYNAMICMODELS
221 Cation substitution and sizemismatch
223 Cation-ordering phenomena
226 Convergent ordering
233 Non-convergent ordering
236 Magnetic contributions
240 Crystalline defects
242 SOLUTIONMODELSFORTHEOXIDEMINERALS
243 Cubic oxides: spinels
252 Rhombohedral oxides
256 Orthorhombic oxides
258 RECOMMENDED STANDARD STATEPROPERTIES
260 OXIDEGEOTHERMOMETERS
260 DIRECTIONS FORFuTURE RESEARCH
262 REFERENCES
Chapter 7 B. J. Wood, J. Nell & A.B. Woodland
MACROSCOPIC AND MICROSCOPIC THERMODYNAMIC
PROPERTIES OF OXIDES
265 INTRODUCTION
266 ACTIVITYMEASUREMENTS
266 Equilibration withmetal
268 Equilibration withnoble metals
268 Interphase partitioning
273 ENTHALPYMEASUREMENTS
273 SPECIFIC SYSTEMS
273 FeO-MgO
274 Otherrocksalt structure oxides
275 Spinel structure oxides
276 Fe304-Fe2Ti04
278 MgA1204-Cr204
278 FeAl204-FeCr204
278 Fe304-FeC[204
279 Fe304-FeAl204
279 FeA1204;MgAl2-Mg2Ti04
x