EARTH AND PLANETARY SCIENCE LEITERS 11 (1971) 1-6.

NORTH-HOLLAND PUBLISHING COMPANY

THE ORTHOPYROXENE GEOBAROMETER

B. J. WOOD and R. G. J. STRENS

Department o f Geophysics and Planetary Physics,
School of Physics, The University,
Newcastle NE1 7R U, England

Received 21 November 1970

Revised version received 16 January 1971

A temperature-composition diagram has been constructed for the system MgSiO3 FeSiO3 at 1 atm, using a
combination of experimental data obtained at 1100 and 1250 ° and thermodynamic calculations. From the informa-
tion contained in this T - X diagram, and that provided by experimental work on the P - T stability field of ortbo-
ferrosilite, and by studies of the distribution of iron between olivine and orthopyroxene, a series of T - X sections of
the system have been calculated for pressures of 0 (X 2.5) to 15 kbars. The ferrosilite content of a metamorphic
orthopyroxene coexisting with quartz and olivine increases by a constant 2.6% Fs per kbar over this pressure range,
and decreases by approximately 1% for each 100 ° increase in temperature.
The T - X sections are thought to be sufficiently accurate to give the absolute pressure of crystallisation to within
1 kbar if the temperature of formation of an olivine-pyroxene-silicaassemblage is known to -+ 100°C. Application
of this geobarometer to the orthopyroxenes of metamorphic rock suggests pressures of crystallisation ranging up to
8.5 kbars. Intermediate values of 3 to 5 kbars are indicated for contact metamorphosed rocks and deep-seated acid
intrusions. The corresponding depths of crystallisation of orthopyroxene-bearing metamorphic rocks are 15 to
35 km ifg has remained constant. In geologically favourable circumstances the geobarometer is sufficiently accurate
to permit secular variations of 1(~o in the universal gravitational constant (G) to be detected.

1. Introduction garnets are complex and largely undetermined. The

There are a number o f examples o f binary solid
solutions in which one component (A) is stable over a
wide range o f pressures, whilst the other (B) is stable
only at high pressures. Under these conditions, the
composition of a saturated solid solution o f B in A at
any given temperature is a sensitive function o f the
pressure of crystallisation. Examples quoted by
Strens [ 1 ] in a recent review o f geothermometry and
geobarometry include enstatite-orthoferrosilite,
a c m i t e - j a d e i t e , a l m a n d i n e - p y r o p e and certain
AI2SiO 5 solid solutions, and others exist, e.g.
j a d e i t e - d i o p s i d e [2]. The behaviour of the a c m i t e -
jadeite system is complicated in many natural samples
by the presence o f large amounts of diopside in solid
solution, leading to the crystallisation o f the structur-
ally complex omphacites. P y r o p e - a l m a n d i n e garnets
commonly contain significant amounts of spessartine
and andradite, and the reaction relations o f these
AI2SiO 5 solid solutions, although binary, are stable
only over a limited pressure range, and they are not
therefore very useful in geobarometry.
By contrast, the enstatite-ferrosilite system is
relatively free o f these problems, since b o t h olivine
and orthopyroxene solid solutions may be regarded as
binary, and there is only one relevant reaction if the
ortho-clino inversion is ignored:
olivine + silica polymorph ~ pyroxene.
The large volume change and small entropy change of
this reaction imply a strong sensitivity to pressure,
combined with insensitivity to temperature, which are
desirable properties o f a geobarometer [1, 3].
Nafziger and Muan [4] have shown that pyroxene
compositions up to Fs57 are stable at 1250°C and
1 atm, and Lindsley [5] and Akimoto et al. [6] have
shown that orthoferrosilite ( F s l 0 0 ) is stable above
2 B.J. Wood, R.G.J. Strens, The orthopyroxene geobarometer
17 kbar at the same temperature, indicating an
average change in pyroxene composition of 2.6% Fs
per kbar. Since the Fs content of orthopyroxene
coexisting with olivine and silica can be determined to
-+ 1%, the orthopyroxene geobarometer is potentially
accurate to -+ 0.4 kbar.
A method of calculating T - X sections at any pres-
sure from appropriate phase equilibrium data and
thermodynamic constants has been developed [7],
and this was first applied to the calculation of a T - X
section at 1 atm from Lindsley's P - T d a t a . The
results, and particularly the slope of the boundary
of the pyroxene field, did not agree with Nafziger and
Muan's results [4], and we have therefore redeter-
mined the 1 atm T - X relations at 1100 and 1250°C,
with results that agree with the calculation.
2. Experimental
Preliminary experiments on pyroxene stability at
1 atm were made with stoichiometric mixtures of
composition MSiO 3 where M = (MgxFe l - x ) ,
prepared from MgO, SiO2, and Fe203 previously
dried at 700°C, and electrolytic iron powder dried at
120°C (analysis: 99.47% Fe). The mixture was ground,
pressed into pellets, and held in sealed iron capsules
for 1 to 2 days at 1100 or 1250°C. The sintered
pellets were darkened by unreacted wtistite. This
partial failure to react was attributed to the fact that
many oxide grains in a stoichiometric mixture would
not be within diffusion range of a silica grain if(as is
probable) the mean diffusion distance (d) is com-
parable with the mean grain size (~). Later experi-
ments therefore utilised a mixture with a considerable
excess of silica (1MO:2SiO2) , yielding colorless
pellets after a day at 1100°C. Optical and X-ray
examination confirmed that reaction of oxides with
silica was complete. Pellets were ground, pressed, and
re-run until no further change in the intensity or
spacing of the olivine (130) reflection was discernible.
There was some metastable persistence of olivine in
the pyroxene field, the amount decreasing with run
time, and with increasing proportion of excess silica.
The olivine (130) peak was of normal width, implying
a close approach to homogeneity in most samples.
The reaction products were identified optically,
and by X-ray methods. Olivine compositions were
obtained from the (130) spacing, using the SnO 2
(I01) reflection as an internal standard [8], and by
analysis with the electron probe. In the absence of a
reliable method of determining the composition of
small pyroxene grains, the Fs content was assumed to
correspond to the initial Fe/(Fe + Mg) ratio,
provided magnesiowustite and olivine were absent. In
an attempt to grow pyroxene crystals large enough
for accurate probe analysis, some runs were made at
1250°C using small amounts of sodium tetraborate as
a flux. These runs yielded pyroxene plus glass, and
set a lower limit of Fs54 on the maximum Fs content
of pyroxene at this temperature, since the reaction
silica + borate flux -~ liquid has negative AG.
Cristobalite and clinopyroxene rather than tridym-
ite and orthopyroxene were the dominant polymorphs
formed in these experiments. Both pyroxene and
olivine crystallise during the early stages of sintering
and it is not strictly necessary to reverse the reactions
as all the phases involved are present throughout.
However, one sample (Fs57.5) was first equilibrated at
1 I O0°C in the pyroxene field, and then held at
1250°C in the 3-phase region: olivine grew, confirm-
ing the location of the boundary.
3. Results
The results of the experiments at 1 atm are shown
in fig. 1, where they are also compared with data
obtained by other workers. Agreement with the
pyroxene field determined by Nafziger and Muan [4]
is good at 1250°C, but the divergence increases at
lower temperatures. We attribute this in part to the
diffusion effects noted earlier, and partly to the wide
(5% Fs) spacing of the experimental points in the
earlier work. Smith's data [9] (corrected to 1 atm)
are in reasonable agreement with ours, although we
suspect that some of his runs using pyroxene as
reactant may exhibit metastable persistence of
pyroxene into the 3-phase field, and some low tem-
perature runs with olivine + silica apparently failed to
react: possibly £ > d at these temperatures.
4. Calculation of T - X sections at high pressure
The problem is to calculate AG as a function of
 B.J. Wood, R.G.J. Strens, The orthopyroxene geobarometer
(P, T, X) for the reaction:
(Fe, Mg)2SiO 4 + silica ~ (Fe, Mg) (Mg, Fe)Si206 .
(1)
The reaction has been written in this way to empha-
size the quasi-ideality of olivine, and the non-
ideality of orthopyroxene, in which iron is strongly
ordered into the M(2) position. The thermodynamic
properties of both phases depend sensitively on the
way in which the Fe and Mg are distributed between
the M(1) and M(2) positions, and we start by relating
the thermodynamic properties to the site populations,
and to the exchange energies which determine these
populations.
Consider the intersite exchange equilibrium:
Fe 2+Mg 1 ~-Fe I +Mg 2 .
The partition coefficient, assuming ideal solution
within each cation lattice is:
K12 = [Fe 2] [Mgl]/[Fe 1] [Mg2]
where the [Fei] and [Mgi] are the appropriate
atomic fractions. The standard free energy change for
this exchange reaction is then:
AG12 =-RTlnK12
and
AGI2 ~, AtHcf- T~hSel + constant
where ncf is the crystal field stabilisation enthalpy,
Sel is an electronic entropy contribution arising from
the distribution of the iron 3d electrons over the five
3d orbitals, and the constant contains electrostatic and
strain energy terms. Given accurate structure data,
each of these terms can be calculated, providing a
useful check on the experimental values of AGI2 [7].
The first step in the calculation of AG for reaction
(1) is the estimation ofAG~ I and AG~I~x, i.e. the
exchange energies which characterise the intracrystal-
line distributions (Fe-Mg order) in olivine and ortho-
pyroxene. Both X-ray [10] and phase equilibrium
studies [4] suggest that AG~1 as defined before is
negligible for minerals crystallised near 1200 °, 1 atm.
However, our calculations from structure data [7]
3
suggest a slight preference of iron for M(2), and there
is also some evidence of ordering from Mossbauer
work [ 11 ]. For the present, we assume AG~ = 0,
i.e. that olivine forms a quasi-ideal binary solid
solution.
By contrast, the Fe-Mg distribution in ortho-
pyroxene is strongly ordered, with iron preferring the
M(2) position. The data obtained by Virgo and
Hafner [ 12], who equilibrated orthopyroxene at
500 to 1000°C, quenched, and determined the result-
ing intersite distribution of iron by the Mossbauer
method, yield 14 < G ~ x < 19 kjoule/mole. Similar
values are obtained from the experimentally deter-
mined distributions of iron between orthopyroxene
and olivine [13, 14] and by calculation from the
structure data. The value adopted here is 18. I kjoule/
mole at 1000°C and 1 atm.
The intracrystalline exchange energies being
known, it is then necessary to calculate the energies
for exchange between pseudo-ideal olivine and the
orthopyroxene M(I) and M(2) positions. These have
been obtained by fitting isotherms through the
distribution data obtained by Medaris [ 13 ] and by
Grover and Orville [14]. The results agree with
calculations [7] from structure data to within
2 kjoule/mole:
AGo 1 = G°l _ VMl~°PX= _ 14.8 kjoule/mole
AG02 = G61 -
~opx = + 3.3 kjoule/mole
VM2
both at 1000°C and 1 atm. The standard free energy
change of reaction (1)may then be written:
AG ° = AsU° - T A S ° + P A V - T ( S °l - S~cPX)
+ AG01x 1 + AG02x 2
where AU° and AS° are the standard internal energy
and entropy changes for the reaction of pure ortho-
ferrosilite to fayalite plus silica, the S c are the
entropies of mixing of(Fe, Mg) in olivine and ortho-
pyroxene, and the x i are the iron contents of the
M(I) and M(2) positions in orthopyroxene.
The calculations of(T, X) sections were based on
the assumption that AG = 0 at Fs62, 1 atm, 870°C
(fig. 1). The ortho-clino inversion was ignored in the
calculation as the energy terms are insignificant. Other
4 B.J. Wood, R.G.J. Strens, The orthopyroxene geobarometer
D ~3oc
Jz,~
\ "%3---- -m
\ \ D S
rnpg \
mOI"
x\
\
50 60
Fig. I. Temperature-compositiondiagramofpa~ of the
En.-Fs systemat I arm. The ortho-clino inversionhas been
ignored. Diamond symbolsgive the compositionof olivine
(from d 130, and electronprobe analysis)and pyroxene
(electron probe analysisof pyroxenefrom fluxed run) of
limiting compositions.The rectanglesrepresentthe composi-
tions of the reactants.The boundariesof the olivine and
pyroxene fields determined by Nafziger and Muan are shown
for comparison (NM), as are Smith's data (S) for those runs
which showed definite evidence of reaction of pyroxene to
olivine + silica (or vice-versa). To render the results directly
comparable, the Fs content of Smith's reactants has been
shifted towards the origin by 2.6% Fs pei"kilobar for those
runs made at 0.5 or 1.0 kbar.
thermodynamic data, notably molar volumes,
thermal expansion coefficients, and compressibilities
are taken from refs. [8], [15] and [16]. The volume
change of reaction (1) was assumed linear between
3.60 cm 3 for Mg2Si206 and 4.22 cm 3 for Fe2Si206.
Olivine, pyroxene, and a silica polymorph are in
equilibrium for those (P, T, X) values for which AG
of reaction (1) is zero. These points were located by
plotting AG against pyroxene composition at some
chosen pressure and temperature. Temperature and
pressure were incremented independently in steps o f
100 ° and 2.5 kbar respectively, each pair o f (P, 7')
values yielding one X for which AG = 0. The resultant
graph (fig. 2) shows the movement o f the boundary
of the pyroxene field as the pressure is increased.
At constant temperature, the variation in the iron
content o f pyroxene coexisting with olivine and
quartz is nearly linear, averaging 2.6% Fs per kbar at
1100°K. At constant pressure, the ferrosilite content
decreases by l to 2% Fs for each 100 ° increase in
temperature, the decrease being larger in the tri-
dymite field. Over most of the (T, X) range, a deter-
mination of the Fs content to + 1%, with the tem-
"c
IIoc T
90C
-5
-6 70C
50C
"6
70 %FS % FS 60 70 80 90 I00
Fig. 2. Temperature-composition sections of the En-Fs
system at pressures from 1 atm to 15 kbar, showing the move
ment of the boundary of the pyroxene field to higher Fs
contents with increasing pressure. The fields of low (~) and
high (#) quartz, and of tridymite (T) are indicated. The
boundary of the pyroxene field is slightly displaced from
that shown in fig. 1 by the application of a correction for
the presence of metastable cristobalite, rather than stable tri-
dymite, in our run products. Smith's run (S) with Fs95 at an
uncorrected pressure of 12.5 kbar and 9000(2 is plotted for
comparison with the calculated 12.5 kbar isobar. The result
of our hydrothermal run at 2.00 kbar, 7500(2 is also shown
(WS): run time was 2 weeks using Fe:Fe304 buffer.
perature of crystallisation known to + 50 ° gives the
pressure o f crystallisation to -+ 0.5 kbar, plus any
systematic errors in our calibration. The following
evidence seems to indicate that systematic errors are
small: first, the calculation fits both the observed
1 atm T - X section (fig. l ) a n d Lindsley's [5] P - T
stability curve for orthoferrosilite within the experi-
mental error. Second, electron probe analyses o f large
olivine and pyroxene crystals grown hydrothermally
at 2.00 kbar, 750°C, are in excellent agreement with
calculated values (fig. 2). Third, Smith [9] found
Fs95 to be stable above an uncorrected pressure o f
12.5 kbar, at 900°C, and this point plots on the
calculated 12.5 kbar isobar. Finally, the pressures o f
crystallisation calculated below appear geologically
reasonable. We conclude that the error in our cali-
bration is largely determined by the errors in the
available experimental data, rather than errors in the
assumptions made, or in the calculation.
5. Effect of additional ions on pyroxene stability
The replacement o f (Fe, Mg) in M(2) by large ions
 B.J. Wood, R. G.J. Strens, The orthopyroxene geobarometer
such as Ca and Mn, and of (Mg, Fe) in M(1) by A1 or
other small ions affects the observed distributions in
at least three ways. The first is a simple blocking ef-
fect, which can be allowed for in the calculations by
reducing the pyroxene site multiplicities from 1 to
( 1 - x ) , where x is the mole fraction of the blocking
ion. The effect of a substitution on the relative
stability of the pyroxene and olivine structures is
much more difficult to evaluate, particularly when a
heterovalent substitution such as 2Al for Mg + Si is
involved, but the formation of pyroxene appears to
be favoured in all cases, and the presence of large ions
in M(2) probably stabilises clino-relative to ortho-
pyroxenes. Finally, the phase capable of accommo-
dating the larger amount of a third ion (Ca, Mn, Al)
is stabilised by the larger entropy of mixing. The
blocking effect tends to reduce the Fe:Mg ratio,
whilst the "structural" and "entropy" effects increase
this ratio: the net result is an extension of the stability
field of pyroxene to higher Fs contents, especially at
high tempe~'atures. The monoclinic iron-rich pyroxenes
from lunar rocks [17] may exemplify this, pyroxenes
near Wo25 En 5 Fs70 having crystallised at ~ 1125°C
and low pressure.
6. Applications of the orthopyroxene geobarometer
Excluding minerals containing > 2.5 mole percent
of Ca, Mn, or octahedral Al in solid solution (rather
than in lamellae), the highest iron contents have been
reported for metamorphic orthopyroxenes from
eulysites, a number of which have 77 to 88% Fs.
Assuming the temperature of formation of these
rocks to have lain in the range 200-700°C, then the
pressures of crystallization were 4 to 9 kbar, implying
depths of 15 to 33 krn. Detailed petrographic studies
of pyroxenes from the Biwabik complex [18] in
which iron-rich rocks were metamorphosed at the
contact with a large basic intrusion, show that early
orthopyroxene (Fs77) coexists with quartz and
olivine (Fa9 l). The temperature of crystallisation has
been determined by oxygen isotope thermometry as
700 to 750°C. From fig. 2, the pressure of crystallisa-
tion was 5.0 kbar, corresponding to a depth of 18 kin.
Finally, orthopyroxene (Fs70-75) coexists with
olivine (Fa90) and quartz in a batholithic adamellite
from southern Natal [ 19], indicating a pressure of
5
3.5 kbar if the temperature of crystallisation was
800°C.
The determination of palaeogravity, and thus of
the secular variation (if any) of the universal gravita-
tional constant is of considerable importance to the
development of cosmological theories, and theories of
planetary origin. On Dirac's postulate [20] that
G ¢~ T - 1, a 20% change in G would have occurred
during the last 2000 my. The orthopyroxene geo-
barometer is sufficiently sensitive to detect this
change. Geological conditions favourable to the
application of this method will not be common
[1, 21] but the preferred method is to use:
GM 10OAFs , 2
r E - g = 2.6--~-~ m/sec
where AFs is the difference in iron content (in % Fs),
and Ah the vertical separation (in kin), at the time of
crystallisation, of two orthopyroxene-olivine-quartz
assemblages. The right conditions for the application
of this method might be provided by an intrusion
several kilometers thick, with thermally metamor-
phosed iron-rich rocks top and bottom, e.g. Biwabik
I18].
7. Discussion and conclusions
The importance of developing continuous-scale
geothermometers and geobarometers to replace the
discontinuous scales embodied in the concepts of the
metamorphic facies and the petrogenetic grid has
been emphasised by Strens [1]. The orthopyroxene
geobarometer appears to be one of the best of the
possible continuous scale geobarometers, and ortho-
pyroxene-olivine-quartz assemblages are common
enough for the technique to be applied to such
problems as the determination of palaeogeothermal
gradient and palaeogravity [ 1], pressures of formation
of rocks, and even to checking experimentally
determined (P, 7) relations, such as those between the
AI2 SiO 5 minerals.
The computational techniques developed in this
work are now being applied to reactions of very com-
plex systems such as almandine-pyrope + silica (four
ferromagnesian phases, six inequivalent sites) and
cummingtonite + silica + water (four phases, eight
6 B.J. Wood, R.G.J. Strens, The orthopyroxene geobarometer
sites). Apart from their use in g e o t h e r m o m e t r y and
geobarometry, the ability to calculate (T, X) sections
tbr such systems promises a very substantial reduction
in the n u m b e r of experimental runs required to reach
a desired degree of precision. For example, experi-
mental runs on c u m m i n g t o n i t e w o u l d have to be
spaced at intervals of 2% in F e / ( F e + Mg) and 5°C
in T to reveal the fine detail in the calculations, but
with calculated (T, X) sections available tile experi-
ments can be planned to give the m a x i m u m of infor-
m a t i o n from the m i n i m u m n u m b e r of runs.
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