Phase Diagrams of Earth-Forming Minerals

Dean C. Presnall

The purpose of this compilation is to present a selected For several of the mineral groups, only representative
and compact set of phase diagrams for the major Earth- phase diagrams are shown. (2) The presentation of more
forming minerals and to show the present state of knowl- complex phase diagrams that show mutual stability
edge concerning the effect of pressure on the individual relationships among the various minerals and mineral
mineral stabilities and their high-pressure transformation groups has been minimized. (3) Many subsolidus phase
products. The phase diagrams are arranged as follows: diagrams important to metamorphic petrology and
thermobarometry are excluded. Reviews of these
Figure subsolidus phase relationships and thermodynamic data for
Silica 1 calculating the phase diagrams have been presented
Feldspars 2-7 elsewhere [13, 50, 70, 122, 1541. Other useful reviews and
Pyroxenes 8-13 compilations of phase diagrams are Lindsley [96] for
Olivine 14-16 oxides, Gilbert et al. [60] and Huckenholz et al. [74] for
Garnet 17-20 amphiboles, Liu and Bassett [104] for elements, oxides,
Iron-titanium oxides 21-23 and silicates at high pressures, and Phase Diagrams for
Pargasite 24 Cerumists [129-1371. It will be noted that some diagrams
Serpentine 25 are in weight percent and others are in mole percent; they
Phlogopite 25 have usually been left as originally published. Minor
Iron 26-27 drafting errors and topological imperfections that were
found on a few of the original diagrams have been
The compilation has been compressed in three ways. (1) corrected in the redrafted diagrams shown here.

D. C. Presnall, University of Texas, Dallas, Geoscience Pro-

gram, POB 830688, Richardson, TX 7.5083-0688

Mineral Physics and Crystallography

A Handbook of Physical Constants
AGU Reference Shelf 2

Copyright 1995 by the American Geophysical Union. 248

 PRESNALL 249

Pressure, GPa
5 10 15
Pressure, GPa Fig. 2. Isopleth for the composition, NaAlSigOs [12, 16,
331. The albite = jadeite + quartz reaction shown by Bell
Fig. 1. Phase relationships for SiO2. Numbers beside
and Roseboom [12] and in this figure is about 0.1 GPa
curves refer to the following sources: 1 - [178]; 2 - [168]; 3 higher than the curve of Boettcher and Wyllie [22]. The
- [160]; 4 - [4]. The melting curve is from Jackson [77] at ,latter passes through the “consensus” value of 1.63 GPa,
pressures below 4 GPa, from Kanzaki [83] at pressures 600°C for this reaction [81]. Also, the quartz-coesite curve
between 4 and 7 GPa, and from Zhang et al. [178] at
shown by Bell and Roseboom [12] and in this figure is
pressures above 7 GPa. The temperature of the high
about 0.4 GPa higher at 1300°C than the pressure given by
quartz-low quartz-coesite invariant point is from Mirwald a linear extrapolation of the curve of Bohlen and Boettcher
and Massonne [ 1131. The quartz-coesite transition is from [24], which is shown in Figure 1. The curve of Bohlen and
Bohlen and Boettcher [24] but note that their curve lies
Boettcher would intersect the albite = jadeite + quartz
toward the low-pressure side of the range of curves by
curve at about 1300°C rather than the jadeite + quartz
others [5, 23, 31, 62, 89, 1131. The high quartz-low quartz
(coesite) = liquid curve. At about lOOO”C, Liu [loll
curve is from Yoder [172]. Boundaries for the tridymite
synthesized NaAlSigOg in the hollandite structure at
and cristobalite fields are from Tuttle and Bowen [164]
pressures from 21 to 24 GPa, and a mixture of NaAlSi04
except that the cristobalite-high quartz-liquid invariant
(CaFezOa-type structure) + stishovite above 24 GPa.
point has been shifted to 0.7 GPa to accomodate the data of
Jadeite, NaAlSi206; Coesite, SiO2.
Jackson [77]. Silica has been synthesized in the FezN
structure at 35-40 GPa, T>lOOO”C by Liu et al. [105], and
at 35 GPa, 500-1000°C by Togaya [162]. However,
Tsuchida and Yagi [ 1631 reported a reversible transition
‘“““I’
between stishovite and the CaC12 structure at 80-100 GPa
and T> 1000°C.

Fig. 3. Isopleth for the composition, CaAI;?SizOs [67, 941.

Cor, corundum; Gr, grossular; Ky, kyanite; Qz, quartz; Liq, 1000 I I I ,/ , I I I
liquid. Locations of dashed lines are inferred. 0 I 2 3 4
Pressure, GPO
250 PHASE DIAGRAMS

Leucite + Liquid

High Sanidine

IIOO-
I I I I I I I I _
0 I 2 3 4
Pressure, GPa

Fig. 4. Isopleth for the composition, KAlSi30s [93, 1491. At 12 GPa, 900°C Ringwood et al. [144]
synthesized KAlSi3Os in the hollandite structure. In experiments from 8-10 GPa and 700”-lOOO”C, Kinomura
et al. [88] synthesized the assemblage K2Si409 (wadeite-type structure) + kyanite (A12Si05) + coesite (SiO2)

from the composition KAlSi30s; and they synthesized the hollandite structure of KAlSi3Os at 9OO”C, 12 GPa,
and at 700°C 11 and 11.5 GPa.
An
CaAlzSizOe

Ab Or
NaAISi,OB Mole percent KAISi,O,

Fig. 5. Compositions of coexisting alkali feldspar and plagioclase at 0.1 GPa and temperatures from 800 to
9OO”C, as indicated [49]. Note that the phase boundary is essentially isothermal except in the Ab-rich portion
of the diagram. Many others have discussed ternary feldspar geothermometry [lo, 39, 54, 58, 63, 66, 75, 80,
139, 142, 151-153, 1651 and ternary feldspar phase relationships [68, 121, 156, 164, 1751. An, anorthite; Ab,
albite; Or, orthoclase.
 PRESNALL 251

1800 I I I 1 I I 1 I I
I

1700-

Liquid t Corundum _
1600 -

Liquid +
Corundum

I I I I I I I I I
7001 60 70 80 9gaA, si o
IO 20 30 40 50
NaAlSi308 Mole Percent 2 28
Anorthite
Albite

Fig. 6. Temperature-composition sections for the join NaAlSigOs (albite) - CaA12Si208 (anorthite) under
anhydrous conditions at 1 atm [26, 1171, 1 GPa, 2 GPa [33, 941, and under H20-saturated conditions at 0.5
GPa [79, 1751.
252 PHASE DIAGRAMS

130(

Liquid
120(
Leucite t Liquid
/

I lO(

Feldspar + Liquid

lOO( Feldspar

Liquid t Vapor
/ /

Orthoclase t Liquid tVapor

70(

t
Orthoclase tVapo
Vapor
/
2 Feldspars + Vapor
60(

50( II
Na*lSi,Or 20 30 40
Weight
50 60
percent
\

70 80 90
KAISi,O,

Fig. 7. Temperature-composition sections for the join NaAlSigOg (albite) - KAlSi308 (orthoclase) under
anhydrous conditions at 1 atm [148], and under HZO-saturated conditions at 0.2 GPa [29] and 0.5 GPa [ 119,
1751. Ab, albite; Liq, liquid; V, vapor. Locations of dashed lines are inferred.
 PRFBNALL 253

Orthoenstatite

Protoenstatite

5 IO 15 20 25
Pressure, GPa

Fig. 8. Isopleth for the composition MgSi03 [7, 9, 35, 45, 56, 57, 65, 76, 92, 127, 140, 1691. For additional
data at pressures above 15 GPa, see also Sawamoto [147]. Not shown is a singular point at about 0.13 GPa
below which enstatite melts incongruently to forsterite + liquid [45]. Position of dashed curve is inferred. For
additional data on melting temperatures up to 58 GPa, see Zerr and Boehler [ 1771.

Fig. 9. Melting curve for diopside, CaMgSi& Curve 1 is

from Williams and Kennedy [ 1661 uncorrected for the
effect of pressure on thermocouple emf, and curve 2 is
from Boyd and England [33]. See also Yoder [173] for
data below 0.5 GPa. For CaMgSi206 composition, Mao et
al. [ 1lo] found a mixture of perovskite (MgSi03) and glass
at 21.7 and 42.1 GPa and lOOO”-1200°C. They interpreted
I I I I
the glass to be a second perovskite phase of CaSi03
13001 I
I 2 3 4 5 composition which inverted to glass on quenching [see also
Pressure, GPa 1021.
254 PHASE DIAGRAMS

1601

I atm 20 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’
II?Gt II + CaSi03Pv

CM _

CaSiL3Pv

-. C;x + Gt
0
$ 14 -.

Di
+ _
a CaSi03 Pv
.‘CPX

IO -_
Pen + Di

I 1
3p 5c I
Di
60Casio
-3
Mole percent Casio,
\ Oen + Di
‘Oen
Fig. 12. Pressure-composition section for the system
I I I I I I I I’

Mg,SI,OB 2o 40 60 80 CaMgSi,Oe MgSiOs-CaSQ at 1650°C [55, 571. Garnet and

Mole
Fig. 10. The join MgzSi206 (enstatite) - CaMgSi206
(diopside) at 1 atm [43]. Many others have also discussed
phase relationships on this join [9, 14, 36, 41, 42, 56, 78,
91, 106, 170, 1711. Fo, forsterite, MgzSi04; Liq, liquid;
Pen, protoenstatite; Opx, orthopyroxene; Pig, pigeonite; Di,
diopside; Oen, orthoenstatite.
percent clinopyroxene, when they are free of Ca on the left-hand
margin of this diagram, are the same phases, respectively,
as majorite and high-P clinoenstatite on Figure 7. 11,
ilmenite; Gt, garnet; Pv, perovskite; Cpx, clinopyroxene;
Opx, orthopyroxene; Di, diopside; CM, a high-pressure
phase of unknown structure.

u Oen + Di
\

Fig. 11. Thermodynamically modeled subsolidus phase

relationships for the system Mg2Si206 (enstatite) -
CaMgSi206 (diopside) from I.5 to 10 GPa [56, 441. The
8OOV
Mg,Si,O, 20 40 60 80 CaMgSi,O,
thermodynamic models are based on data from other
sources [37, 98, 118, 123, 128, 1501. See also data of
Mole percent Biggar [ 151 from 1 atm to 0.95 GPa.
 PRESNALL 255

Mole percenl
Fig. 13. Orthopyroxene + augite, orthopyroxene + augite + pigeonite, and pigeonite + augite equilibria at 1
atm and 500-1300°C [95]. Phase relationships to the right of the forbidden zone boundary are metastable
relative to augite + olivine + silica. Lindsley [95] has presented three other similar diagrams at 0.5, 1, and 1.5
GPa. Lindsley and Andersen [97] should be consulted for correction procedures required before plotting
pyroxenes on these diagrams for geothermometry. En, enstatite (MgSi03); Fs, ferrosilite (FeSiO3); Di,
diopside (CaMgSi206); Hd, hedenbergite (CaFeSi206).

Periclase + Liquid
2500 1
Anhydrous

ite
ie

Spine1

Forsterite

1 /I:

/ / Spine1 \ ]

-L I / I

5
Pressme, G Pa

Fig. 14. Isopleth for the composition Mg2SiOd [48, 57, 1411. Additional studies of the melting relationships
are Ohtani and Kumazawa [126] and Kato and Kumazawa [84-861. Locations of dashed lines are inferred.
 2000
Llquld
t

Pyrope
iti
E I400
c OLIVINE

1300-
1000 I
I /
I200 - 0 I 2 3 ;essure, 5 6 7 8 9 IO
GPo

Mg,?,o, IO 20 30 40 50 60 70 80 90 Fe,S,O, Fig. 17. Isopleth for Mg3A12Si3012, pyrope garnet. Phase
Weight percent
relationships at pressures less than 5 GPa are from Boyd
Fig. 15. Phase relationships for the system Mg2Si04 and England [32]. The melting curve at 5 GPa and above
(forsterite) - FezSiO4 (fayalite) in equilibrium with Fe at 1 is from Ohtani et al. [125]. Liu [99] reported that pyrope
atm [27]. Locations of dashed lines are inferred. transforms to perovskite + corundum at about 30 GPa, 200-
800°C. Liu [loo] subsequently revised this result and
found that pyrope transforms to the ilmenite structure at
, I , , , , , , ,
PvtMw I1 1 /&j-Pv+Mw+St
/&LPv+Mw+St
about 24-25 GPa, lOOO”-14OO”C, and that ilmenite then
25- transforms to perovskite at about 30 GPa. Locations of
dashed lines are inferred.

SP
I- PV
Pv + Gt
\ P\

\ Gt 1

Al:o,
Gt

\
\
\

Mg,SIO, 20 40 60 80 Fe,!?10~ 101 1 1 1 1 1 1 1 h k 1 ’ ’ I

Mole percent MgSiO, 5 IO 15 20 25 30 AI,O,

Fig. 16. Pressure-composition sections for the join Mole percent AI,O, ” -
Mg2Si04-Fe2Si04 at various temperatures. Phase Fig. 18. Pressure-composition section for the join MgSiOj-
relationships above 21 GPa are from Ito and Takahashi Al203 at 1000 and 1650°C [57, 821. For additional data
[76] and those below 21 GPa are from Akaogi et al. [3]. along the boundary between the garnet and clinopyroxene
Other references [51, 87, 1571 give additional data and + garnet fields at 1OOO”C,see Akaogi and Akimoto [2]. At
discussion of these phase relationships. Pv, perovskite 1100 and 1600°C for pressures between 2 and 6.5 GPa, the
(MgSiOg-FeSiO3 solid solution); Mw, magnesiowiistite A1203 content of pyroxene in equilibrium with garnet
(MgO-Fe0 solid solution); St, stishovite (SiO2); Sp, spinel; increases with decreasing pressure to at least 15 mole
Mod Sp, modified spinel; 01, olivine. percent [30, 341.
 PRESNALL 257

A’,03
Corundum

1200 OC, 3 GPa

CaSiO, CaMgSi,O, MgSiO,

Wollastonite Diopside Enstatite
Weight percent

Fig. 19. The system CaSi03-MgSi03-Al203 at 12OO”C,3 GPa [30]. Co, corundum; Di, diopside; Ca-Gt, Ca-
garnet; Mg-Gt, Mg-garnet; Wo, wollastonite; En, enstatite; CaAl$i06, Ca-Tschermak’s molecule.

Pyrope
+- Grossular,

GPa
GPa

Diopside Mole % CaSiO, MgSiO,

Fig. 20. Compositions (unsmoothed) of coexisting garnet (Gt), Ca-rich pyroxene (Cpx), and Ca-poor
pyroxene (Opx or Cpx) at various pressures and temperatures [69]. Labels of the type, 9, 2000, indicate
pressure (GPa) followed by temperature (“C). Pyrope, Mg3Al$Si3012; Grossular, Ca3A12Si3012.
258 PHASE DIAGRAMS

I /I
L.IQUID Fe

--I”- .-
i’
AIR
..-.- -

- - py(f=JF.. “J ,cB
-.
)-
n!
(u 1200 -‘-‘~ \, /
2 k-/-l., 7. -.--pJ
y- lDrlhl + \A/iicTlrc
u
“+IaJ t -.-.- -.- .-.-

.-.-.-
800- CY-IRON + WkTlTE .-.-.- ,p-.-
__.-.-
-.- ,$!L- -
.-.-.- ,p?-. -
.~ _-_-_-I pL.- -.- ,6’1.-
600--‘-.- .-.-. -. - lC24- ,o-14-.-
,@C.-
-.-.- - .-.__. -.-.-.-.- ,g?-., - .-,Cj-E- .- -
I-.-.- (/!L.--.-.-.-.-.- -.-ic3L. - .- ,0-l” .- -
Cl!- IRON + MAGNETITE -.- -
I 1 1 -L- -I I I lC20-. -
Fe 0.1 0.3 Fe0 23 24 25 26 27 FesO, 29 Fe,O,
Weight % Oxygen

Fig. 21. Temperature-composition section for the system Fe-O at 1 atm [46,47, 64, 120, 1381. Light dash-dot
lines are oxygen isobars in atm.
 PREBNALL 259

Rutile
TiOo

1300°c
One atm
1 * .

Mole percent Hem

Fig. 22. The system TiOz-FeO-FqO3 at 13OO”C, 1 atm [161]. Light dashed lines are oxygen isobars labeled
in log oxygen fugacity units (atm). Psb, pseudobrookite (FezTiOs); Fpb, ferropseudobrookite (FeTi205); Ilm,
ilmenite (FeTiOs); Hem, hematite (FezOg); Usp, ulvospinel (FezTi04); Mt, magnetite (Fe304); Wiis, wiistite
(Fed3
260 PHASE DIAGRAMS

o”-1: i
k
0-

-:

-2c )

Temperature, “C
Fig. 23. Temperature-oxygen fugacity (&) grid for coexisting magnetite-ulvospinel solid solution and
ilmenite-hematite solid solution pairs [ 1551. Lines with labels of the type, I-70, indicate mole % ilmenite in
the ilmenite (FeTiOs) - hematite (Fe203) solid solution. Lines with labels of the type, U-70, indicate mole %
ulvospinel in the ulvospinel (Fe2Ti04) - magnetite (Fe304) solid solution. Mt, magnetite; Usp, ulvospinel;
Ilm, ilmenite; Hem, hematite.
 PRESNALL 261

Pa-out
/ I
400 800 1000 1200 IL IO
Temperature”C

Fig. 25. Pressure-temperature projection showing the upper

temperature stability limits for serpentine, Mg$i205(OH)4
(curves I and 2) and phlogopite, KMg3AISi30to(OH)2
(curves 3-6). Numbers beside curves refer to the following
sources: 1 - [28]; 2 - [90]; 3-6 - [115]. Curves 5 and 6 give
the maximum stability of phlogopite in the presence (curve
5) and absence (curve 6) of vapor. Curves 3 and 4 give the
corresponding maximum stability of phlogopite in the
/ ‘Pa-out (0.5) presence of forsterite and enstatite, and represent more
,< , , , / , , closely the stability of phlogopite in the mantle. Curves 3-
800 900 1000 1100 1200 1300 1400 I 5oc
6 are not univariant [114]. See Yoder and Kushiro [174]
Temperature,“C for an earlier study of the stability of phlogopite. Montana
and Brearley [ 1161 speculated that a singular point exists at
Fig. 24. Pressure-temperature projection of pargasite, (Pa) about 1.5 GPa on curve 4, so that the curve above this
NaCa2Mg4A13Si6022(OH,F)2, stability limits. The pressure is metastable.
univariant curves labeled Pa-out (1 .O), Pa-out (0.5), and Pa-
out (0.3) are from Gilbert [59], Holloway [71], and Oba
[124], and give the maximum stability of pargasite during
melting in the presence of a pure Hz0 or H20-CO2 vapor
with Hz0 mole fractions of 1.0, 0.5, and 0.3. Small
concentrations of other constituents in the vapor are
ignored. The dashed curve labeled OHtnu, and the
patterned areas labeled F430H57 and Ftoo are from
Holloway and Ford [72] and Foley [52], and show the
breakdown of pargasite during vapor-absent melting for
different proportions of fluorine and hydroxyl in the
pargasite.
262 PHASE DIAGRAMS

6000 -

CM IOC

I I
100 200 300
Pressure, GPO

Fig. 27. High pressure melting curves for iron. For

reference to Figure 26 at low pressures, the curves of
Ethcp)
Mirwald and Kennedy [ 1121, Bundy [40], and Boehler [ 171
are used for the a-&-y phase relationships. Numbers beside
melting curves and brackets refer to the following sources:
1 - [I]; 2 - [II]; 3 - [167]; 4 - [25, 381; 5 - [17-19, 21, 103,
143, 1531. Gallagher and Ahrens [54] found that earlier
shock data from their laboratory [ 1l] are 1000°K too high,
which brings the data of Bass et al. [l l] and Brown and
Pressure, GPa McQueen [38] into agreement. The shock data of Yoo et
al. [176] (not plotted but located at 6350 K, 235 GPa and
Fig. 26. Low pressure phase relationships for iron.
6720 K, 300 GPa) are at slightly higher temperatures than
Numbers beside curves refer to the following sources: 1 -
the data of Brown and McQueen. (Ross et al. [145] and
[159]; 2 - [109]; 3 - [112]; 4 - [103]; 5 - [6]; 6 - [20,40]; 7 -
Anderson [8] have proposed the existence of a new phase,
[107]; 8 - [73]; 9 - [17, 211. Several additional references
al-iron, that is stable along the liquidus at pressures above
[61, 108, 1791 also discuss the WE transition,.
about 170 GPa. On the basis of molecular dynamics
calculations, Matsui [ 11 l] has also proposed the existence
of a new phase at 300 GPa and temperatures above 5000 K.
Acknowledgements. Preparation of this compilation was
supported by Texas Advanced Research Program Grants 009741- Saxena et al. [146] have suggested that al-iron is the
007 and 009741-066, and by National Science Foundation Grants liquidus phase down to a pressure of 60-70 GPa. CM,
EAR-8816044 and EAR-9219159. Contribution no. 738, core-mantle boundary (136 GPa); IOC, inner-outer core
Geosciences Program, University of Texas at Dallas. boundary (329 GPa); C, center of Earth (364 GPa).

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 PRESNALL 263

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