Physics of the Earth and Planetary Interiors 143144 (2004) 469479

Phase relationships and equations of state for FeS

at high pressures and temperatures and implications for the
internal structure of Mars
Satoru Urakawa
a,
, Keiko Someya
a
, Hidenori Terasaki
b,1
, Tomoo Katsura
c
,
Syo Yokoshi
c
, Ken-ichi Funakoshi
d
, Wataru Utsumi
e
, Yoshinori Katayama
e
,
Yu-ichiro Sueda
f
, Tetsuo Irifune
f
a
Department of Earth Sciences, Okayama University, Okayama 700-8530, Japan
b
Geoscience Institute, University of Tsukuba, Tsukuba 305-8571, Japan
c
Institute for Study of the Earths Interior, Okayama University, Misasa 682-0193, Japan
d
Japan Synchrotron Radiation Research Institute, Mikaduki 679-5198, Japan
e
Japan Atomic Energy Research Institute, Mikaduki 679-5198, Japan
f
Geodynamic Research Center, Ehime University, Matsuyama 790-8577, Japan
Received 12 February 2003; received in revised form 24 November 2003; accepted 1 December 2003
Abstract
In situ X-ray diffraction experiments on FeS up to 22 GPa and 1600 K were carried out using large volume multianvil
apparatus, combined with synchrotron radiation at SPring-8. We investigated phase stability relationships of FeS and deter-
mined the straight phase boundaries between FeS III (monoclinic phase) and FeS IV (hexagonal phase) to be T (K) = 20P
(GPa) +170 and between FeS IV and FeS V (NiAs-type phase) to be T (K) = 39.6P (GPa) +450. We also found anomalous
behavior in the c/a ratio, thermal expansion, and isothermal compression of FeS V as well as FeS IV, in the pressure range
412 GPa. These anomalies in FeS can be attributed to the spin-pairing transition of Fe, and divides FeS IV and FeS V into
the high-spin low-pressure phase (LPP) and the possibly low-spin high-pressure phase (HPP). In order to investigate the
internal structure of Mars, we evaluated the equations of state for FeS IV (HPP) and FeS V (HPP). A least square t to the
experimental data yielded K
0T
= 62.5 0.9 GPa at T = 600 K and (dK
0
/dT)
P
= 0.0208 0.0028 GPa/K for FeS IV
(HPP), and K
0T
= 54.3 1.0 GPa at T = 1000 K and (dK
0
/dT)
P
= 0.0117 0.0015 GPa/K for FeS V (HPP) with xed
K

= 4. Thermal expansion coefcients were = 7.16 10

5
+6.08 10
8
T for FeS IV (HPP) and = 10.42 10
5
for
FeS V (HPP), respectively. Using these equations of state, we examined the internal structure of Mars that has a model mantle
composition [Meteoritics 20 (1985) 367] and FeFeS core. Our models show that an Mg-silicate perovskite-rich lower mantle
is stable only with the Fe-rich core having less than 20 wt.% sulfur. The polar moment of inertia factor C derived from Mars
Pathnder data [Science 278 (1997) 1749] is consistent with any compositions between Fe and FeS for the Martian core, but
it excludes the presence of a crust thicker than 100 km.
2004 Elsevier B.V. All rights reserved.
Keywords: Iron sulde; Spin transition; Martian core; Bulk modulus; Thermal expansion

Corresponding author. Tel.: +81-86-251-7885; fax: +81-86-251-7895.

E-mail address: urakawa@cc.okayama-u.ac.jp (S. Urakawa).
1
Present address: Bayerisches Geoinstitut, University of Bayreuth, D-95440 Bayreuth, Germany.
0031-9201/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.pepi.2003.12.015
470 S. Urakawa et al. / Physics of the Earth and Planetary Interiors 143144 (2004) 469479
1. Introduction
Iron sulde (FeS) has been thought to be one of the
major constituents of the cores of terrestrial planets
such as Mars. Phase stability relations and density of
FeS at high pressure and high temperature are fun-
damental to evaluate the internal structure of planets
having a sulfur-bearing core, especially Mars (e.g.,
Fei et al., 1995; Kavner et al., 2001). However, uncer-
tainties in Martian interior models are still large due
to the ambiguity of phase stability elds and inaccu-
racy in the density of FeS. Thus, we require accurate
phase relationships and equations of state for FeS at
pressures and temperatures corresponding to the deep
interior of Mars and other planets.
FeS is known to undergo several structural and
electro-magnetic phase transformations up to 25 GPa
and between 300 and 1000 K (e.g., Taylor and Mao,
1970; King and Prewitt, 1982; Fei et al., 1995; Kusaba
et al., 1997, 1998a,b, 2001; Kobayashi et al., 1997;
Rueff and Kao, 1999; Takele and Hearne, 1999;
Urakawa et al., 2002). Troilite (FeS I), a stable
stoichiometric FeS phase at ambient condition, has
a superstructure of the NiAs-type structure with a
hexagonal unit cell (

3a, 2c), where a and c are the

fundamental unit cell parameters of the NiAs-type
structure. Room temperature compression of FeS
causes the successive phase transition of FeS I into
FeS II (MnP-type phase) at 3.4 GPa and then into FeS
III (monoclinic phase) at 6.7 GPa (King and Prewitt,
1982; Fei et al., 1995; Kusaba et al., 1997, 1998a,b).
Mssbauer spectroscopy and X-ray emission spec-
troscopy revealed that FeS III adopts a low-spin state
conguration of Fe, and the structural phase transition
of FeS II to FeS III involves the electronic transition
from a high-spin state to a low-spin state (Kobayashi
et al., 1997; Rueff and Kao, 1999; Takele and Hearne,
1999). Above room temperature, FeS transforms to
FeS IV and then to FeS V with increasing temperature
in the pressure range 020 GPa (e.g., Urakawa et al.,
2002). FeS IV has a hexagonal NiAs-type super-
structure with a (2a, c) unit cell, whereas FeS V
shows the simple NiAs-type unit cell (Fei et al.,
1995). Fei et al. (1995) and Kusaba et al. (1998b)
found anomalous behaviors during compression of
FeS IV, in which the isothermal compression curve
is inected and the c-axis is abruptly shortened
around 7 GPa. Both authors speculated that these
anomalies can be attributed to the electronic transi-
tion of FeS IV without any structural change. It is,
therefore, worth elucidating whether FeS V shows
similar high-pressure behavior as FeS IV, because
the high-temperature phase is dominant in plane-
tary interiors. We must take the possibility of the
electronic transition into consideration in order to
evaluate the equation of state for FeS relevant to the
interior of Mars. In this study, we examine the phase
relationships of FeS and the equations of state for
FeS IV and V using in situ X-ray diffraction obser-
vation and propose models of the internal structure
of Mars.
2. Experiments
Experiments were performed at SPring-8, using
large volume high-pressure apparatus: SMAPII at
BL14B1 and SPEED-1500 at BL04B1 (Utsumi et al.,
1998). SMAPII is a 180 t DIA-type cubic press,
which was used for experiments up to 10 GPa, and
is equipped with six WC anvils with a 3 mm anvil
truncation and a boron-epoxy resin pressure trans-
mitting cube with a 6 mm edge length. SPEED-1500,
a KAWAI-type 68 double stage apparatus driven
by 1500 t press, was used for experiments at higher
pressures than 10 GPa. A set of WC cubic anvils
with a 3 mm truncated edge length and MgO octa-
hedral pressure transmitting medium with a 9 mm
edge were used. High temperature was generated by
resistance heating using a graphite tube heater below
10 GPa and a titanium carbidediamond sheet heater
above 10 GPa. Sample temperature was measured by
a W97%Re3%W75%Re25% thermocouple, and the
effect of pressure on emf was ignored.
Starting material was polycrystalline FeS (troilite),
which was synthesized from pure Fe and S sealed in an
evacuated glass tube at 903 K for 2 weeks (Morimoto,
1976; King and Prewitt, 1982). The unit cell param-
eters of the troilite were a = 5.969(1) and c =
11.760(6) . The chemical formula of the troilite was
determined to be Fe
0.999
S from the d
1 1 4
value (Yund
and Hall, 1969). The powdered FeS (510 m grain
size) was mixed with powdered NaCl in a 1:1 volume
ratio, and then packed in an hBN sample container.
NaCl was used as the pressure standard, and also
acted as a diluent to prevent grain growth of FeS at
S. Urakawa et al. / Physics of the Earth and Planetary Interiors 143144 (2004) 469479 471
high temperature and to reduce the deviatric stress on
the sample.
X-ray diffraction was conducted by an energy dis-
persive method using white X-rays up to 150 keV with
a Ge solid state detector, in a transmitting geome-
try. The Bragg angle was xed at 4.5

or 5

to cover
the main diffraction peaks of the FeS polymorphs and
NaCl. The typical exposure time was 5 min, providing
the data of sufcient quality for phase identication
and unit cell parameter evaluation. X-ray diffraction
proles of the powdered mixture of FeS and NaCl were
acquired at the position close to the hot junction of the
thermocouple. Sample pressures were evaluated from
the unit cell volume of NaCl using Browns equation
of state (Brown, 1999).
First, the sample was pressurized by applying oil
pressure to a target value. Next, the sample was heated
to the highest desired temperature at a given oil pres-
sure, in order to minimize the effects of deviatoric
stress on the observed unit cell parameters. Then the
500
1000
1500
0 10 20
T
e
m
p
e
r
a
t
u
r
e

/

K
Pressure / GPa
FeS V
FeS I
FeS III
FeS IV
Liquid
(HPP)
(LPP)
(HPP)
(LPP)
FeS II
1.635
1.64
1.65
1.65
1.68
1.66
1.69
1.67
1.64
Fig. 1. Summary of the phase identications obtained by in situ X-ray observations and the stability elds of FeS polymorphs with the
iso-c/a ratio curves (thin lines) of the fundamental NiAs unit cell. Open squares are FeS I (troilite), open diamonds are FeS III (monoclinic
phase), solid circles are FeS IV (hexagonal phase), and open circles are FeS V (NiAs-type phase). FeS II was not found in this study (see
text). Iso-c/a ratio curves are consistent with those of Kusaba et al. (1998b) who reported iso-c/a ratio curves up to 10 GPa and 700 K.
The curve with c/a = 1.64 at low pressure is constrained using data of Kusaba et al.
sample temperature was decreased to room tempera-
ture at a constant oil pressure, with X-ray diffraction
patterns of the sample being acquired at an interval of
100 K. This procedure was repeated to the maximum
press load, and X-ray diffraction patterns of FeS were
collected at about 150 pressure and temperature con-
ditions up to 22 GPa and 1600 K.
3. In situ X-ray diffraction observations and
stability of FeS polymorphs
We observed four stable phases, FeS I (troilite),
FeS III (monoclinic phase), FeS IV (hexagonal
phase), and FeS V (NiAs-type phase) by in situ X-ray
diffraction experiments up to 22 GPa and 1600 K.
We, however, could not nd FeS II, which was re-
ported to be stable between FeS I and FeS III at
room temperature (e.g., King and Prewitt, 1982;
Fei et al., 1995; Marshall et al., 2000). FeS II was
472 S. Urakawa et al. / Physics of the Earth and Planetary Interiors 143144 (2004) 469479
40 60 80 100 120
FeS IV
I
n
t
e
n
s
i
t
y
Energy / keV
16.0 GPa, 500 K
2.3 GPa, 500 K
7.4 GPa, 500 K
2
0
0
0
0
2
2
0
1
2
0
2
2
2
0
1
0
3
3
2
1
0
0
2
2
2
1
3
0
1 2
0
3
0
0
2
1
1
0
1
1
2
N
a
C
l

1
1
1
N
a
C
l

2
2
0
N
a
C
l

2
0
0
M
g
O

2
2
0
M
g
O

2
0
0
T
C
N
a
C
l

2
0
0
N
a
C
l

2
0
0
N
a
C
l

2
2
0
N
a
C
l

2
2
0
h
B
N

0
0
2
h
B
N

0
0
2
1
0
1
1
0
1
1
0
1
2
0
0
2
0
0
2
0
1
2
0
1
2
0
2
2
0
2
2
2
1
3
0
1
3
0
1
2
2
0
2
2
0
2
0
3
2
0
3
1
0
3
40 60 80 100 120
FeS V
I
n
t
e
n
s
i
t
y
Energy / keV
19.4GPa, 1300 K
3.3 GPa, 1300 K
8.5 GPa, 1300 K
1
0
0
0
0
2
1
0
1
1
0
2
1
1
0
1
0
3
2
0
1
2
2
0
1
0
0
0
0
2
1
0
1
1
0
2
1
1
0
1
0
3
1
0
0
0
0
2
1
0
1
1
0
2
1
1
0
1
0
3
N
a
C
l

1
1
1
N
a
C
l

2
2
0
N
a
C
l

2
0
0
M
g
O

2
2
0
M
g
O

2
0
0
T
C
N
a
C
l

2
0
0
N
a
C
l

2
0
0
N
a
C
l

2
2
0
N
a
C
l

2
2
0
h
B
N

0
0
2
h
B
N

0
0
2
Fig. 2. Examples of X-ray diffraction spectra of FeS IV (hexagonal phase) and FeS V (NiAs-type phase) at high temperatures and high
pressures. Crystal structures of FeS IV and V are not affected by anomalous compression behavior between 4 and 12 GPa.
always detected during room temperature compres-
sion, but it was not observed when the temperature
was decreased from the stability region of FeS IV
(Kusaba et al., 1997, 1998a,b; Urakawa et al., 2002).
Kinetic barriers might hinder the transformation of
FeS IV into FeS II during cooling. Based on X-ray
diffraction proles, we determined the phase bound-
aries between the four FeS phases, as shown in
Fig. 1.
X-ray diffraction patterns (Fig. 2) clearly show that
FeS V, with a simple NiAs-type structure, is stable
up to at least 22 GPa at temperatures higher than the
stability eld of FeS IV. The boundary between FeS
IV and FeS V is dened as a straight line, T (K) =
39.6P (GPa) + 450. The straight phase boundary is
more consistent with that reported by Kusaba et al.
(1998a) rather than the curved boundary predicted by
Fei et al. (1995), but has a shallower slope than the
previous estimate (47.2 K/GPa, Kusaba et al., 1998a).
Combined with the melting curve of FeS reported by
Boehler (1992), an extrapolation of the IVV bound-
ary constrains the IVV liquid triple junction to lie
at 50 GPa and 2400 K. This suggests that the simple
NiAs-structured FeS V can exist as a stable phase
up to 50 GPa. This is consistent with the results of
SR-DAC experiments (Kavner et al., 2001), which
showed that FeS V is stable up to 35 GPa above
1500 K.
Low-spin congurated FeS III (monoclinic phase)
is stable above 7.5 GPa as a low temperature
phase. The phase boundary between FeS III and
IV is determined to be T (K) = 20P (GPa) + 170
(Fig. 1). The slope of the IIIIV boundary is con-
sistent with that reported by Fei et al. (1995),
but the absolute temperature is lower by about
50 K.
S. Urakawa et al. / Physics of the Earth and Planetary Interiors 143144 (2004) 469479 473
4. Isostructural phase transition of FeS
IV and FeS V
Anomalous high-pressure behavior of FeS IV
was reported by Fei et al. (1995) and Kusaba et al.
(1998b). In both these studies, it was found that the
isothermal compression curve of FeS IV cannot be
dened by a single equation of state and FeS IV ex-
ists as two phases, a low-pressure phase (LPP) and
a high-pressure phase (HPP). They also reported an
abrupt change in the c/a ratio of FeS IV, correspond-
ing to an inection of the compression curve. An
anomaly was also found in the thermal expansivity
of FeS IV by Kusaba et al. (1998b, 2001), who re-
ported that thermal expansivity has a minimum at
5.7 GPa. In both studies, these phenomena were at-
tributed to an electronic transition of FeS IV without
structural change, in which the spin conguration of
Fe changes from the high-spin state to the low-spin
state. Although this interpretation has not been con-
ned yet, the electronic state of FeS III, stable phase
at room temperature above 7 GPa, strongly supports
this hypothesis.
We found similar anomalies not only in FeS IV
but also in FeS V. Isothermal compression curves for
both FeS IV and FeS V can be divided into three
parts separated by two inections (Fig. 3): a high-spin
LPP region, a transient region, and possibly a low-spin
HPP region. High-pressure phases of both FeS IV and
FeS V are clearly denser than the low-pressure phases.
Inection points seem to move toward higher pressure
with increasing temperature. Hereafter, we denote the
low-pressure and the high-pressure phases of FeS IV
and V as FeS IV (LPP), FeS V (LPP), FeS IV (HPP),
and FeS V (HPP), respectively.
The observed changes in the c/a ratio of FeS IV
along the isothermal compression curve at 500 K are
consistent with those reported by Fei et al. (1995) as
shown in Fig. 4(B). The change in the c/a ratio of
FeS V at 1200 K is small and unclear (Fig. 4(A)),
but iso-c/a ratio curves in Fig. 1 show that FeS IV
(LPP) and FeS V (LPP) have larger interlayer dis-
tances than FeS IV (HPP) and FeS V (HPP). At pres-
sures above 10 GPa, the c/a ratios of HPP are close to
ideal closed-packed values and increase slightly with
temperature from 1.63 at 500 K to 1.64 at 1300 K.
This means that the linear thermal expansivity along
the c-axis is larger than that along the a-axis. On the
0.80
0.90
1.00
V

/

V
0
FeS V (LPP)
FeS V (HPP)
FeS IV (HPP)
T = 1200K
(A)
0 5 10 15 20 25
0.80
0.90
1.00
Pressure / GPa
V

/

V
0
FeS IV (LPP)
FeS IV (HPP)
T = 500K
(B)
Fig. 3. Isothermal compression curves of FeS at 1200 K (A) and
500 K (B). Solid circles are FeS IV and open circles are FeS V.
Open squares in (B) are data for FeS IV at 473 K from Kusaba et al.
(1998b). Dashed lines are compression curves for the high-pressure
phases calculated by using the parameters listed in Table 1. Solid
lines have been drawn as guides for the eye. Compression data
for each phase can be divided into three parts; the low-pressure
phase (LPP) region, a transient region, and the high-pressure phase
(HPP) region.
other hand, the iso-c/a curves are complex in the LPP
region and the transient region below 10 GPa.
We calculated the isobaric thermal expansivities
of FeS IV and V by tting a linear equation to the
volume data at constant pressure (Fig. 5). Combined
with the data from Kusaba et al. (1998b, 2001), a
steep depression of thermal expansivity of FeS IV
was observed in the pressure range 49 GPa. FeS
V also shows an anomalous pressure dependence of
thermal expansivity below 9 GPa, which increases
with pressure between 4 and 9 GPa by a factor of
2. On the other hand, above 9 GPa, the thermal ex-
pansivities of both FeS IV (HPP) and FeS V (HPP)
have similar values and decrease monotonously with
pressure.
474 S. Urakawa et al. / Physics of the Earth and Planetary Interiors 143144 (2004) 469479
1.62
1.64
1.66
1.68
1.70
0 5 10 15 20 25
c

/

a
Pressure / GPa
T = 500 K
1.62
1.64
1.66
c

/

a
T = 1200 K
(A)
(B)
Fig. 4. The c/a ratios for the fundamental NiAs unit cell of FeS
plotted along the isothermal compression curves at 1200 K (A)
and 500 K (B). Closed circles are FeS IV and open circles are FeS
V. Open squares at 500 K are data from Fei et al. (1995), which
are consistent with our results.
This high-pressure behavior indicates that both FeS
IV and FeS V undergo pressure induced isostructural
phase transitions. While the compression curves and
the c/a ratios indicate that this phase transition pro-
ceeds in the pressure range 59 GPa for FeS IV and
712 GPa for FeS V, thermal expansivities show that
the transient region of FeS V is identical to that of
FeS IV and lies between 4 and 9 GPa. All anomalous
behavior correlates with the interlayer distance in the
fundamental NiAs unit cell, and occurs in the tran-
sient region between the LPP stability eld and the
HPP stability eld. If this isostructural transition of
FeS is due to the electronic transition of Fe from the
high-spin state to the low-spin state, the two electronic
states might be mixed in the transient region and the
proportions of the electronic state might change with
both pressure and temperature. In this case, anomalous
thermoelastic properties of FeS IV and FeS V can be
explained by the interaction between Fe atoms along
the c-axis of the fundamental NiAs unit cell.
0.0
4.0
8.0
12.0
0 5 10 15 20 25

/

1
0
-
5

K
-
1
Pressure / GPa
Fig. 5. Pressure dependence of the volume thermal expansivity
of FeS. Solid circles are FeS IV, open circles are FeS V, and
solid diamonds are data for FeS IV from Kusaba et al. (1998b,
2001). For the calculation of thermal expansivity, we used the data
obtained at a constant pressure (0.2 GPa).
Anomalies in FeS IV and FeS V affect not only
thermoelastic properties but also phase relationships
in the system including FeS. Inections of the eu-
tectic melting curves in the FeFeS binary system
and the FeFeSFeO ternary system in the pressure
range 510 GPa (Usselman, 1975; Fei et al., 1997;
Urakawa et al., 1987) must correlate with the isostruc-
tural phase transition from FeS V (LPP) to FeS V
(HPP).
5. Equations of state for FeS IV (HPP)
and FeS V (HPP)
As shown above, thermoelastic properties of FeS IV
and FeS V change over the pressure range 412 GPa.
For applications to the deep interior of the terrestrial
planets, density data for FeS IV (HPP) and FeS V
(HPP) are necessary. We evaluate high-temperature
equations of state for FeS IV (HPP) and FeS V (HPP)
using the volume data determined above 11.7 GPa us-
ing SPEED-1500 at BL04B1.
We tted the following BirchMurnaghan equation
of state to the volume data:
S. Urakawa et al. / Physics of the Earth and Planetary Interiors 143144 (2004) 469479 475
Table 1
Parameters of equations of state for FeS IV (HPP) and FeS V
(HPP)
FeS IV FeS V
T
0
(K) 600 1000
K
0T
(T
0
) (GPa) 62.5 0.9 54.3 1.0
dK
0
/dP
a
4.0 4.0
dK
0
/dT (GPa/K) 0.0208 0.0028 0.0117 0.0015
V
0
(T
0
)
b
(
3
) 228.02 0.41 59.92 0.15

0
(10
5
K
1
) 7.16 0.51 10.42 0.49

1
(10
8
) 6.08 1.31
a
This parameter is xed to be 4.0 in least square tting.
b
Unit cell volume for FeS IV (Z = 8) and for FeS V (Z = 2).
P(V, T) =
3
2
K
0T
(T)
_
_
V
V
0
(T)
_
7/3

_
V
V
0
(T)
_
5/3
_

_
1
3
4
_
4
_
K
0
P
_
T
_
_
_
V
V
0
(T)
_
2/3
1
__
(1)
K
0T
(T) = K
0T
(T
0
) +
_
K
0
T
_
P
(T T
0
) (2)
V
0
(T) = V
0
(T
0
) exp
__
T
T
0
dT
_
(3)
Thus, bulk modulus, its temperature derivative, ther-
mal expansivity, and the unit cell volume at 0.1 MPa
and T
0
for both FeS IV (HPP) and FeS V (HPP)
were determined by a non-linear least squares t
with a xed pressure derivative of the bulk modu-
lus dK
0
/dP = 4. We did not use volume data from
near the phase transition pressure in this procedure.
We assumed the temperature dependency of thermal
expansivity to be =
0
+
1
T, and calculated
for both temperature-dependent and -independent
cases. Parameter data sets, that are consistent with
the experimentally determined phase boundary be-
tween FeS IV and FeS V, are K
0T
= 62.5 GPa at
T = 600 K, (dK
0
/dT)
P
= 0.0208 GPa/K, and
= 7.16 10
5
+ 6.08 10
8
T for FeS IV (HPP)
and K
0T
= 54.3 GPa at T = 1000 K, (dK
0
/dT)
P
=
0.0117 GPa/K, and = 10.42 10
5
for FeS V
(HPP) (Table 1). Equations of state at 500 and 1200 K
are shown in Fig. 3 together with the experimental
data.
Bulk modulus and thermal expansivity of FeS IV
(HPP) were also determined in previous studies by Fei
et al. (1995) and Kusaba et al. (1998b). The former
study gave K
0T
= 54 6 GPa at T = 800 K, which
is consistent with our value of 58.3 GPa at 800 K,
whereas the latter reported a signicant lower value
of K
0T
= 49 2 GPa at T = 573 K. Kusaba et al.
(1998b) used volume data close to the phase transition
pressure in their t, so that their K
0T
is relatively low
due to the large volume change near the phase bound-
ary, as shown in Fig. 3. Our estimation of thermal ex-
pansivity for FeS IV (HPP) is slightly larger than that
of Fei et al. (1995).
The present study rstly reports the thermoelastic
properties of FeS V (HPP). The bulk modulus and
thermal expansivity of FeS V (HPP) are close to those
of FeS IV (HPP), because the phase transition between
FeS IV and V is at a second order (Kusaba et al.,
2001). The equation of state for FeS V (HPP) can be
compared with the density data reported by Kavner
et al. (2001), which were determined by a laser-heated
SR-DAC technique. The reported density of FeS V
(HPP) of 5.96 Mg/m
3
at 17 GPa and 1600 K is clearly
higher than the present result of 5.75 Mg/m
3
by 4%,
corresponding to a temperature difference of 500 K
at constant pressure. We suggest that Kavner et al.
(2001) may have overestimated the density of FeS V
(HPP) due to a large temperature error associated with
laser heating.
6. Implications for the structure of the Martian
interior
Studies of the internal structure of Mars have
been based on cosmochemical models combined
with high-pressure experiments (Ohtani and Kamaya,
1992; Kamaya et al., 1993; Fei et al., 1995; Bertka
and Fei, 1997, 1998a,b; Kavner et al., 2001; Sanloup
et al., 2002), assuming an Fe-rich mantle and an
FeFeS core. Estimated density proles of the Mar-
tian mantle are consistent with each other and there
is a consensus on the Martian mantle structure, al-
though there has been a debate concerning whether
or not Mars has an Mg-silicate perovskite-bearing
lower mantle. The presence of an Mg-perovskite layer
would inuence the thermal history of Mars, because
this layer controls the mode of mantle convection and
476 S. Urakawa et al. / Physics of the Earth and Planetary Interiors 143144 (2004) 469479
acts as a stable thermal boundary layer at the base of
the mantle. A recent value of the dimensionless polar
moment of inertia factor C = 0.36620.0017, evalu-
ated from Mars Pathnder data (Folkner et al., 1997),
constrains the bulk composition of Mars. Bertka and
Fei (1998a,b) showed that models of the interior of
Mars that are consistent with C determined from the
Mars Pathnder data are not consistent with a chon-
dritic bulk Fe content or Fe/Si ratio. On the other
hand, Zharkov and Gudkova (2000) argued that the
addition of H to the FeFeS core and the reduction of
the Fe number of the mantle make a chondritic bulk
composition possible. This controversy arises mainly
from uncertainties in the density proles of the Mar-
tian core. Previous work on the density of FeS at high
pressures (Fei et al., 1995; Kavner et al., 2001) was
semi-quantitative and there were large uncertainties
in the density estimation at Martian core conditions.
The present study of the equations of state of FeS IV
(HPP) and FeS V (HPP) provides an opportunity to
examine the Martian interior models with an Fe-rich
mantle and an FeFeS core with improved accuracy.
In order to evaluate the internal structure of Mars,
we adopt the Bertka and Fei (1998a) density model
for the Martian mantle. In this model, a mantle com-
position, which was derived from the chemical com-
position of the SNC meteorites (Dreibus and Wnke,
1985), was assumed and the density proles were cal-
culated along the temperature distribution in the Mar-
tian interior determined by Longhi et al. (1992). Our
results show that FeS V (HPP) is a stable phase un-
der the Martian core conditions proposed by Longhi
et al. (1992). The FeFeS binary system, however,
may have a eutectic melting relation at the pressures
of the Martian core (e.g., Fei et al., 2000). Thus, the
density of liquid FeFeS must be taken in account, but
is not available in the required pressure range. There-
fore, we used the density of a mixture of -Fe and FeS
V (HPP) instead of the liquid density for intermediate
compositions in the FeFeS system. This assumption
should be appropriate because the density difference
between liquid and solid in FeFeS system is expected
to be very small at high pressures due to the gentle
Clapeyron slope of the melting curve (e.g., Urakawa
et al., 1987). We used the equation of state for -Fe by
Besson and Nicol (1990), which is consistent with the
volume data reported by Boehler et al. (1989, 1990)
and Funamori et al. (1996).
0
1
2
3
4
0
10
20
30
40
50
0 1000 2000 3000
G
r
a
v
i
t
y

/

m

s
-
2
P
r
e
s
s
u
r
e

/

G
P
a
Depth / km
Fe
FeS
(B)
Gravity
Pressure
4
6
8
10
(A)
D
e
n
s
i
t
y

/

M
g

m
-
3
Fe
Fe-14wt%S
FeS
Fe-25wt%S
Fig. 6. Internal structure models for the Mars. (A) Density distri-
bution proles for four different core compositions with a 50 km
thick crust. Mantle density is from Bertka and Fei (1998a). (B)
Gravity and pressure in the Marian interior corresponding to Fe
(solid line) and FeS (dashed line) core models in (A). Pressure in
the Martian core largely depends on its composition.
Using these data, we calculated internal models
of Mars that satisfy its mass and radius for given
core compositions (from Fe to FeS), crustal den-
sity (3.0 Mg/m
3
) and crustal thicknesses (from 0 to
150 km). We did not constrain the moment of inertia
factor and bulk Fe/Si ratio in the calculations. Fig. 6
shows density, gravity and pressure proles of the
Martian interior with 50 km thick crust. For a given
core composition, there are clear trade-offs between
the core radius and pressure in the core. Pressure at
the center of Mars changes by about 10 GPa with
increasing S content, from 36.3 GPa for a FeS core to
46.1 GPa for a pure Fe core, which is consistent with
previous estimates by Schubert and Spohn (1990).
The results of the present calculations are summarized
in Table 2, including bulk Fe content, Fe/Si ratio, and
moment of inertia factor.
S. Urakawa et al. / Physics of the Earth and Planetary Interiors 143144 (2004) 469479 477
Table 2
Calculated bulk Fe content, bulk Fe/Si weight ratio, core mass fraction (M
core
), core radius (R
core
), pressures at CMB (P
CMB
) and the
center of Mars (P
C
), polar moment inertia factor (C) for Mars models with given core composition and crustal thickness (h
crust
)
Core composition h
crust
(km) Bulk Fe (wt.%) Fe/Si M
core
(wt.%) R
core
(km) P
CMB
(GPa) P
C
(GPa) C
Fe 0 23.7 1.29 11.4 1239 26.4 45.4 0.3656
Fe14 wt.% S 0 24.0 1.35 14.0 1410 24.0 41.2 0.3665
Fe25 wt.% S 0 24.3 1.41 17.0 1568 21.9 38.4 0.3674
FeS
a
0 24.4 1.49 21.1 1750 19.7 36.0 0.3688
Fe 50 24.2 1.32 11.9 1259 26.3 46.1 0.3638
Fe14 wt.% S 50 24.5 1.39 14.7 1433 23.9 41.7 0.3647
Fe25 wt.% S 50 24.8 1.46 17.9 1593 21.7 38.8 0.3657
FeS 50 24.9 1.54 22.1 1779 19.4 36.3 0.3672
Fe 100 24.7 1.36 12.6 1280 26.3 46.8 0.3618
Fe14 wt.% S 100 25.1 1.43 15.6 1459 23.7 42.2 0.3628
Fe25 wt.% S 100 25.4 1.51 18.8 1619 21.5 39.2 0.3639
FeS 100 25.5 1.60 23.3 1810 19.2 36.6 0.3655
Fe 150 25.4 1.41 13.3 1304 26.2 47.6 0.3597
Fe14 wt.% S 150 25.8 1.49 16.5 1486 23.5 42.7 0.3608
Fe25 wt.% S 150 26.0 1.56 19.8 1648 21.3 39.7 0.3620
FeS 150 26.1 1.67 24.6 1843 18.8 36.9 0.3637
a
FeS includes 36.5 wt.% sulfur.
Spherically symmetrical models of the Martian in-
terior are constrained only by the mean moment of
inertia factor I. The polar moment of inertia factor C
is one of three principal moments of inertia, and is
slightly different fromI. Here we use the polar moment
of inertia C as the constraint for the present model in-
stead of I, because there is certain uncertainty in the
estimated I value (e.g., Zharkov and Gudkova, 2000;
Schubert et al., 2001).
The polar moment of inertia factor C, calculated as
a function of given crustal thickness and core com-
position, is plotted against depth of the coremantle
boundary (CMB) in Fig. 7. The polar moment of iner-
tia factor C depends strongly on both crustal thickness
and core composition, whereas the depth of CMB is
less sensitive to crust thickness and depends mainly
on the core composition. The post-spinel transition
occurs at around 1850 km depth in the Martian man-
tle (Fig. 6), so that an Mg-silicate perovskite-bearing
lower mantle appears only when the Fe-rich core con-
tains less than 20 wt.% sulfur, although Kavner et al.
(2001) concluded that the lower mantle exists for a
core composition close to FeS. The polar moment of
inertia factor C = 0.36620.0017 derived from Mars
Pathnder data (Folkner et al., 1997) is consistent with
any compositions between Fe and FeS for the Martian
core, but it excludes a crust thicker than 100 km. A
thick crust is also unlikely from a petrological point of
view if the Martian crust has a basaltic composition,
because this would transform into dense eclogite at a
pressure of 1 GPa (i.e., 90 km in depth). In fact, to-
pography and gravity data, measured by Mars Global
Surveyor mission, provided an estimation of average
crustal thickness of 50 km (Zuber et al., 2000). In this
case, the Martian core must contain more than 10 wt.%
sulfur (Fig. 7).
A notable difference between our study and that
of Bertka and Fei (1998a,b) or Kavner et al. (2001)
is that in the density estimation for the FeS phase.
Bertka and Fei used FeS IV (HPP), instead of FeS
V (HPP), in their models (Bertka and Fei, 1998a,b),
while Kavner et al. (2001) clearly overestimated the
density of FeS V (HPP) as discussed above. Our im-
proved equation of state for FeS V (HPP) gives a lower
density for FeS at Martian core conditions than previ-
ous studies, corresponding to a 100 km difference in
the depth of CMB for a FeS core (Fig. 7). This leads
to a larger bulk Fe/Si ratio at the same sulfur content.
The Fe/Si ratios for the bulk Martian composition cal-
culated in the present models (Table 2), however, are
still smaller than the chondritic value of 1.73, with
the maximum value being 1.60 for a FeS core and a
100 km thick crust, which are within the acceptable
limits constrained by the observed C value.
478 S. Urakawa et al. / Physics of the Earth and Planetary Interiors 143144 (2004) 469479
0.360
0.365
0.370
1600 1800 2000 2200
P
o
l
a
r

m
o
m
e
n
t

o
f

i
n
e
r
t
i
a

f
a
c
t
o
r
Depth of CMB / km
Crustal thickness =
0 km
100 km
150 km
F
e
S
2
5
w
t
%
S
1
4
w
t
%
S
F
e
50 km
Upper limit
Lower limit
BF(FeS)
K(FeS)
BF(Fe)
K(Fe)
Mg-perovskite lower mantle
Fig. 7. Depths of the coremantle boundary of Mars plotted for
several models with different core compositions and crustal thick-
nesses. An Mg-perovskite lower mantle is stable if the Martian
core includes less than 20 wt.% sulfur. Allowable limits of the po-
lar moment of inertia factor C shown as dot-dashed lines (Folkner
et al., 1997) do not constraint the chemical composition of the
Martian core, but exclude a crust thicker than 100 km. Previous
models based on a crustal thickness of 50 km are also shown as
solid circles (Bertka and Fei, 1998a) and solid triangles (Kavner
et al., 2001).
Acknowledgements
The authors would like to appreciate K. Kusaba for
the preparation of troilite sample. They are also grate-
ful to T. Okada for his help in synchrotron radiation ex-
periments. Comments of an anonymous reviewer, P.S.
Balog and D. Rubie helped to improve the manuscript.
This study has been performed under approval of the
advisory committee of SPring-8.
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