Earth and Planetary Science Letters 224 (2004) 415 – 429

www.elsevier.com/locate/epsl

Experimental constraints on the origin of Martian meteorites and

the composition of the Martian mantle
Carl B. Agee *, David S. Draper
Institute of Meteoritics and Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, NM 87131, USA
Received 16 October 2003; received in revised form 12 May 2004; accepted 20 May 2004
Available online

Abstract

The major element compositions of partial melts of a chondritic (Homestead L5) model Mars mantle have been determined
at 4.7 – 5.0 GPa in a multi-anvil device over a temperature interval that ranged from near solidus to near liquidus conditions. The
purpose of these experiments is to determine if the major element abundances of Martian basalts (shergottite meteorites) or their
parent magmas can be derived from a model Martian mantle composition at high pressure. Partial melting of our model
composition at 4.7 – 5.0 GPa produces liquids with super-chondritic CaO/Al2O3 similar to those of proposed Martian basalt
parent magmas. The concentrations of CaO and Al2O3 in the high-pressure experimental liquids are, however, lower than in
Martian basalt parent magmas. We conclude that matches for both ratios and concentrations involving CaO and Al2O3 between
current model Mars compositions and proposed Martian basalt parent magmas would require at least two stages of magmatic
differentiation. For example, partial melting at 5 GPa (425 km depth in Mars) produces a magma having super-chondritic CaO/
Al2O3, but subsequent, lower pressure differentiation of olivine ( F low-Ca pyroxene) is needed to increase the CaO and Al2O3
concentrations to those of calculated Martian basalt parent magmas. This two-stage polybaric differentiation would be
consistent with either a magma ocean or mantle plume-melting scenario. On the other hand, these multi-stage differentiation
scenarios cannot reconcile the significant mismatch between the FeO content of our experimental liquids and Martian basalt
parent magmas. A remedy for this apparent inconsistency might require a bulk Martian mantle or shergottite parent source
region with a composition and Mg# closer to that of H-chondrites, but still much less magnesian than are terrestrial upper-
mantle basalt source regions.
D 2004 Published by Elsevier B.V.

1. Introduction often expressed as superchondritic CaO/Al2O3 [1,2].

One of the most distinctive geochemical character-
istics of Martian basalts and their estimated parent
magmas is a marked aluminum depletion, which is
* Corresponding author.
E-mail address: agee@unm.edu (C.B. Agee).
According to Treiman [3], the shergottite – nahklite –
chassignite (SNC) source region appears to have lost
60% of its primordial aluminum. Fig. 1 shows the
super-chondritic CaO/Al2O3 of several proposed par-
ent magmas for Martian basalts and peridotites. In
contrast, average chondrite values cluster, defining a
very tight range of compositions that have lower
Al2O3 and CaO/Al2O3 than do Martian parent mag-

0012-821X/$ - see front matter D 2004 Published by Elsevier B.V.

doi:10.1016/j.epsl.2004.05.022
416 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429

Fig. 1. Al2O3 versus CaO/Al2O3 (wt.%) diagram illustrating the non-chondritic nature of calculated parent magmas of shergottites and
Chassigny. Am is the parent melt calculated for ALH77005 by McSween et al. [37]; Eg is the parent melt to EETA79001A calculated by Longhi
and Pan [2], and recently recalculated by Schwandt et al. [38]; LEW-ol and LEW-pig are parent melts for LEW88516 calculated by Harvey et al.
[39] assuming olivine and olivine+ pigeonite saturation, respectively; and Sm is the Shergotty parent melt calculated by Stolper and
McSween [40]. Black diamond (labeled DW Mars) is the proposed composition of the Martian mantle by Dreibus and Wänke [4]. Chondrite
compositions are average values for CI1, CM2, CV3, L, LL, and H [31]. Grey circles show bulk rock compositions of shergottite meteorites
[41].

mas. Dreibus and Wänke [4] estimated a bulk com-
position for the Martian mantle (hereafter DW-Mars)
that coincides with the chondritic cluster and is very
close to the composition of L and LL ordinary
chondrites.
Earlier melting experiments on FeO-rich bulk
Mars compositions [5 –9], such as DW-Mars and
others similar to the composition in our current
study, have demonstrated that the super-chondritic
CaO/Al2O3 of Martian parent magmas cannot be
produced by partial melting in the pressure range
1.5 – 3.0 GPa (f 150 – 300 km depth in Mars).
Longhi et al. [10] concluded that the SNC parent
magmas were produced by partial melting of a
garnet-absent, aluminum-depleted source. They pro-
posed that the aluminum could have been removed
from the mantle by successive melting events that
partitioned it into the Martian crust, leaving the
SNC source region Al-depleted. Unfortunately, we
have yet no evidence supporting the existence of
such an aluminum-enriched Martian crust. Further-
more, fractionation processes such as those envis-
aged by Longhi et al. probably cannot account for
the large deviation from chondritic CaO/Al2O3 re-
quired by mass balance for the source region of
Martian parent magmas. For example, low-pressure
partial melting of peridotite depletes the source
region and enriches the crust in both Al2O3 and
CaO, since both components are ‘‘incompatible’’—
hence, large perturbations in CaO/Al2O3 are unlikely
in this process.
Longhi [11] noted that partial melting with garnet
present at 5 –6 GPa might produce Al-depleted mag-
mas and explain the missing Martian aluminum.
However, he cited the melt density measurements of
Agee and Walker [12] on komatiite as evidence that
magmas produced at 5 – 6 GPa in Mars might be too
dense to rise, making a high-pressure genesis for SNC
parent magmas unlikely. In the meantime, Ohtani et
al. [13] showed that Martian mantle melt is in fact
buoyant relative to olivine up to 7 GPa (f 600 km
depth in Mars), and that the melt would be buoyant
relative to a garnet-bearing source region at much
higher pressures than 7 GPa. Thus, magma buoyancy
 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429 417

constraints no longer seem to preclude the existence Table 1

of Martian magma source regions at pressures of at Compositions of starting materials and the DW-Mars for compar-
ison
least 7 GPa, and probably much higher.
Homestead Homestead Dreibus – Wänke
It is now well established from several phase
silicate fraction synthetic Mars
equilibrium studies at P>3 GPa on chondritic com-
SiO2 47.0 45.5 44.4
positions and on Earth mantle peridotites [14 – 16]
TiO2 0.15 0.19 0.13
that increasing pressure up to f 15 GPa continuous- Al2O3 2.68 3.3 2.9
ly expands the stability field of garnet at the expense FeO 16.02 18.35 17.9
of all other crystalline phases, and decreases garnet MnO 0.41 0 0.5
solubility in silicate melt. Hence, it can be expected MgO 29.37 29.04 30.1
CaO 2.1 1.73 2.4
that partial melts at P>3 GPa will be characterized
Na2O 1.12 0.46 0.5
by increasing CaO/Al2O3, approaching values ob- K2O 0.15 0.09 0.04
served in shergottites. Therefore, we were motivated P2O5 0.32 0.4 0.17
to determine whether partial melting of a model Cr2O3 0.66 0 0.8
Martian mantle composition at higher pressures Total 99.98 99.06 99.84
could give rise to shergottites or their parent mag- Homestead silicate fraction from Jarosewich and Dodd [21].
mas. To this end, we present here new data from a Synthetic mixture is the average of f 15 electron microprobe
analyses (20 keV, 40 nA, 50 Am spot size) of quenched
series of super-solidus experiments, done at 4.7 – 5.0 superliquidus run on synthetic Homestead.
GPa, where it was found that garnet coexists with
olivine, low-Ca pyroxene, and silicate liquid. Inter-
estingly, as we describe below, the FeO content and Tb, Yb, Lu, Hf, Y, Sc, and Zr for the experiments of
Mg# (molar Mg/Fe + Mg) of these high-pressure Draper et al. [20]; none of these aliquots had more
liquids, not their CaO/Al2O3, pose the most formi- than 2 wt.% total dopants. For details of the various
dable challenge in explaining the origin of Martian aliquots and trace element partitioning, see [20]. In
basalt parent magmas from model Martian mantle at the current study, we focus on the major element
high pressure. compositions of the 4.7 – 5.0 GPa melts produced in
those same experiments as well as several experi-
ments (labeled AW) in which powders of natural
2. Experimental Homestead were used. Synthetic mechanical mix-
tures were prepared by grinding under ethanol with
2.1. Starting materials an agate mortar and pestle and firing at 500 jC for
approximately 2 h.
Experiments were performed using either synthetic
or natural Homestead L5 ordinary chondrite as the 2.2. Run conditions
starting composition. These starting materials are
good analogs for an FeO-rich Martian mantle and Experiments were run in a Walker-type multi-
are very similar to the bulk Mars mantle composition anvil press at Johnson Space Center using cell
of Dreibus and Wänke [4] and other proposed assemblies, procedures, and calibrations identical to
Martian mantle compositions [17 – 19]. Draper et al. those described by Agee et al. [16]. Tungsten carbide
[20] gave a detailed comparison of Homestead L5 cubes with corners truncated to an 8-mm edge length
and other Mars mantle compositions. Table 1 lists were used with cast, finned octahedra of Aremco
the composition of Homestead L5 [21] normalized Ceramacastn 584 ceramic. The powdered starting
metal-free, and that of our synthetic Homestead materials, stored in a drying oven at f 110 jC
mechanical mixture, prepared from reagent grade between experiments, were placed inside graphite
oxides and carbonates, as well as the DW-Mars capsules with press-fit lids and insulated from the
composition for comparison. rhenium foil heater walls by hard-fired alumina
Various aliquots of synthetic Homestead were sheaths. Capsules were positioned in the center of
prepared by adding subsets of oxides of Nd, Sm, the heater with crushable alumina spacers. Temper-
418 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429

atures were measured by radially inserted W/Re
thermocouples, with the junction near the capsule
at the center of the heater, and controlled by a
Eurotherm 930P programmable controller. Pressures
were applied at 3 – 5 GPa/h. In some of the experi-
ments reported here, to promote growth of larger, but
fewer, crystals, assemblies were typically heated at
350– 500 jC/min to temperatures above the liquidus
at each pressure for 30 –60 min and then cooled to
target temperature over approximately 5 min before
being held at target conditions for 120– 360 min.
These experiments are listed with two temperature
values in Table 2. Runs were quenched by cutting
power to the heater, which caused temperatures to
fall below the glass transition in V 10 s and to room
temperature in less than 5 min. Run conditions are
summarized in Table 2.
2.3. Approach to equilibrium
Achieving chemical equilibrium in multi-anvil
experiments is similar to that of lower pressure pis-
ton-cylinder experiments except that thermal gradients
tend to be more pronounced in the multi-anvil. This
thermal gradient becomes larger with smaller cell
assembly sizes. For example, cell assemblies that are
used for the highest multi-anvil pressures (f 25 GPa)
can have thermal gradients across the sample capsule of
more than 100j. However, in this study, our target
pressures were modest (f 5 GPa) and we were able to
employ a relatively large cell assembly matched to the
8-mm truncation-edge-length-on-cube (TEL) that is
described in Agee et al. [16]. This cell assembly
minimizes the thermal gradient effects by minimizing
capsule size and length and positioning the capsule in
the center of the heater hot spot. The thermal gradient
across the axial length of the sample capsule is
estimated to be less than 50j. This cell has been used
in numerous phase equilibrium, textural equilibrium,
and element partitioning studies (see, for example,
[22 –24]) on a routine basis to f 10 GPa and f 2000
jC. As in these previous studies, our experiments here
represent a close approach to chemical equilibrium.
Compositions of all crystalline phases are nearly
homogeneous, as shown both by electron probe mi-
croanalysis (Tables 3 and 4) and by fairly uniform
backscattered electron images like the one in Fig. 2.
Some zoning occurs in thin (a few micrometers) outer

Table 2
Experimental run conditions
Run Measured T Degree Liquid Liquid Pressure Phases Ol/Liq KD DIW
(C) of melting CaO/Al2O3 Mg# (GPa)
114 1850 superliquidus 0.52 74 4.7 liq
AW4 1850 high 0.83 68 5 liq, ol, opx, met 0.31 0.94
246 1950/1830 high 0.62 65 5 liq, ol, opx 0.36
223 1875/1775 high 0.61 63 5 liq, ol, opx 0.38
AW3 1750 medium 0.96 65 5 liq, ol, opx, gt, met 0.48 1.03
243 1950/1750 medium 1.02 60 5 liq, ol, opx, gt 0.35
150 1775 medium 1.17 57 4.7 liq, ol, opx, gt 0.37
119 1750 low 1.34 54 4.7 liq, ol, opx, gt 0.37
173 1850/1750 low 1.34 49 4.7 liq, ol, opx, gt 0.31
116 1750 low 1.56 49 4.7 liq, ol, opx, gt 0.24
190 1850/1750 low 1.73 46 5 liq, ol, opx, gt 0.31
117 1700 very low nd nd 4.7 liq, ol, opx, gt
AW2 1650 very low nd nd 5 liq, ol, opx, gt, met
AW8 1575 sub-solidus na na 5 ol, opx, gt, met
AW1 1500 sub-solidus na na 5 ol, opx, gt, met
Experiments categorized as ‘‘very low’’ degree of melting had melt pockets and grain boundary films that were too small for electron
microprobe analysis. Hence, no liquid compositional data are reported for these experiments. Runs with ‘‘AW’’ labels were performed on
natural Homestead powder; others on synthetic Homestead (Table 1). Liq = silicate liquid, ol = olivine, opx = low-Ca pyroxene, gt = garnet,
met = iron – nickel – sulfur liquid. Double temperature values are given for experiments that had an initial peak temperature followed by
a lower, constant temperature for the run duration. Ol/Liq KD is the olivine/silicate liquid equilibrium constant and is defined as
XFeO (olivine)  XFeO (liquid)/XMgO (olivine)  XMgO (liquid), where X is the mole fraction. DIW is the oxygen fugacity relative to the iron – wüstite
buffer and is defined as 2log(XFeO/XFe*) where Fe* is defined as XFe (XFe  XS)/(XFe + XNi).
 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429 419

rims that we interpret to have formed during quench-
ing. In all experiments, the quench melt consisted of
an intergrown mass of microlites + glass (Fig. 2).
Quench melt compositions also display reasonable
homogeneity (see standard deviations in Tables 3
and 4), although the totals and standard deviations
of our microprobe analyses were lower and higher,
respectively, than for crystalline phases. In order to
test our assumption of near-equilibrium conditions we
calculated an average of KD = 0.35 F 0.06 (Table 2)

Table 3
Electron microprobe analyses of f 5 GPa run products from synthetic Homestead
Run 150 Run 116
Liq(8) Ol(5) Opx(4) Liq(16) Ol(6) Opx(10) Gt(19)
SiO2 41.9 (1.3) 38.9 (0.2) 55.4 (0.5) 37.4 (1.6) 38.8 (0.1) 55.7 (0.9) 42.7 (0.2)
TiO2 0.58 (0.24) b.d.l. b.d.l. 0.57 (0.08) 0.05 (0.03) b.d.l. 0.14 (0.01)
Al2O3 3.18 (0.05) 0.18 (0.07) 1.91 (0.21) 3.13 (0.37) 0.37 (0.09) 2.01 (0.38) 20.18 (0.22)
FeO 26.8 (0.9) 19.47 (0.30) 10.61 (0.17) 30.2 (1.5) 18.53 (0.27) 10.01 (0.64) 12.24 (0.33)
MgO 19.6 (2.0) 38.6 (0.3) 28.2 (0.3) 16.2 (0.7) 41.1 (0.6) 31.3 (0.8) 21.5 (0.3)
CaO 3.72 (1.09) 0.14 (0.01) 1.05 (0.06) 4.88 (0.16) 0.25 (0.10) 0.80 (0.15) 2.00 (0.07)
Na2O 1.03 (0.21) 0.09 (0.01) 0.30 (0.01) 1.90 (0.18) 0.11 (0.02) 0.29 (0.05) 0.08 (0.03)
K2O 0.23 (0.10) b.d.l. b.d.l. 0.38 (0.08) b.d.l. b.d.l. b.d.l.
P2O5 0.70 (0.35) 0.10 (0.03) b.d.l. 1.50 (0.27) 0.20 (0.08) b.d.l. 0.29 (0.02)
STE oxides none in this run 1.16 0.26 0.02 1.00
Total 97.76 97.48 97.50 97.38 99.72 100.18 100.09
Mg# 56.6 78.0 82.6 48.9 79.8 84.8 75.8

Run 119 Run 173

Liq(13) Ol(4) Opx(6) Gt(6) Liq(23) Ol(5) Opx(5) Gt(24)
SiO2 39.1 (3.2) 38.1 (0.4) 54.8 (0.5) 41.3 (0.2) 36.7 (3.1) 38.2 (0.5) 54.9 (0.4) 40.3 (0.7)
TiO2 0.59 (0.08) b.d.l. b.d.l. 0.18 (0.01) 0.67 (0.13) b.d.l. b.d.l. 0.16 (0.02)
Al2O3 3.65 (0.24) 0.34 (0.15) 2.27 (0.19) 20.18 (0.06) 3.52 (0.37) 0.14 (0.02) 2.40 (0.50) 19.84 (0.55)
FeO 27.0 (2.2) 21.7 (0.2) 11.85 (0.77) 13.87 (0.09) 28.8 (2.9) 22.0 (0.3) 12.72 (0.36) 13.56 (0.28)
MgO 17.76 (0.96) 38.5 (0.6) 28.9 (1.0) 19.28 (0.07) 15.8 (0.8) 39.6 (0.2) 28.9 (0.4) 18.9 (0.4)
CaO 4.88 (0.19) 0.27 (0.17) 1.24 (0.20) 2.68 (0.03) 4.70 (0.43) 0.14 (0.01) 1.22 (0.14) 2.55 (0.09)
Na2O 1.79 (0.36) 0.11 (0.03) 0.44 (0.05) 0.08 (0.01) 1.38 (0.13) 0.08 (0.02) 0.35 (0.03) 0.07 (0.01)
K2O 0.31 (0.15) b.d.l. b.d.l. b.d.l. 0.36 (0.10) b.d.l. b.d.l. b.d.l.
P2O5 1.36 (0.49) 0.14 (0.08) b.d.l. 0.27 (0.03) 1.30 (0.26) 0.08 (0.11) b.d.l. 0.20 (0.03)
STE oxides 1.21 0.04 0.02 1.28 4.67 0.03 0.10 4.75
Total 97.68 99.28 99.46 99.17 97.81 100.36 100.55 100.31
Mg# 54.0 76.0 81.3 71.3 49.4 76.2 80.2 71.3

Run 246 Run 223

Liq(8) Ol(6) Opx(4) Liq(16) Ol(3) Opx(5) Gt(8)
SiO2 40.3 (0.5) 40.3 (0.5) 56.5 (0.1) 43.8 (1.4) 40.8 (0.2) 56.0 (0.5) 43.7 (0.5)
TiO2 0.30 (0.01) b.d.l. b.d.l. 0.29 (0.04) b.d.l. b.d.l. 0.10 (0.03)
Al2O3 4.22 (0.06) 0.18 (0.01) 1.80 (0.07) 4.85 (0.23) 0.21 (0.01) 2.49 (0.72) 19.51 (0.66)
FeO 22.7 (0.3) 15.04 (0.30) 8.72 (0.25) 21.3 (1.4) 16.04 (0.01) 8.92 (0.83) 10.22 (0.65)
MgO 24.1 (0.4) 45.0 (0.7) 32.9 (0.2) 20.6 (0.8) 40.7 (0.1) 29.9 (0.9) 21.7 (0.6)
CaO 2.61 (0.10) 0.07 (0.01) 0.49 (0.01) 2.98 (0.18) 0.09 (0.01) 0.65 (0.12) 1.45 (0.25)
Na2O 0.55 (0.07) 0.05 (0.01) 0.17 (0.01) 0.89 (0.09) 0.06 (0.00) 0.21 (0.05) 0.04 (0.01)
K2O 0.10 (0.01) b.d.l. b.d.l. 0.22 (0.06) b.d.l. b.d.l. b.d.l.
P2O5 0.62 (0.03) 0.09 (0.06) b.d.l. 0.86 (0.16) 0.08 (0.01) b.d.l. 0.23 (0.07)
STE oxides 3.03 0.17 0.26 1.70 0.02 0.05 2.47
Total 98.60 100.84 100.83 97.56 98.07 98.23 99.38
Mg# 65.5 84.2 87.1 63.3 81.9 85.6 79.1
(continued on next page)
420 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429

Table 3 (continued)
Run 243 Run 190
Liq(7) Ol(4) Opx(4) Gt(4) Liq(8) Ol(9) Opx(10) Gt(13)
SiO2 36.0 (1.6) 37.8 (0.6) 53.9 (0.2) 40.9 (0.5) 38.7 (2.0) 37.8 (0.4) 55.7 (0.5) 41.4 (0.7)
TiO2 0.43 (0.04) b.d.l. b.d.l. 0.13 (0.02) 0.65 (0.03) b.d.l. 0.03 (0.01) 0.17 (0.02)
Al2O3 3.34 (0.30) 0.15 (0.01) 1.96 (0.22) 18.33 (1.87) 2.97 (0.55) 0.19 (0.02) 1.88 (0.14) 18.57 (0.76)
FeO 26.2 (1.3) 17.86 (0.47) 10.63 (0.10) 12.24 (0.39) 29.7 (3.6) 24.4 (0.3) 13.82 (0.23) 14.92 (0.27)
MgO 21.9 (0.8) 42.6 (0.5) 31.1 (0.4) 21.9 (1.7) 14.30 (1.94) 38.3 (0.3) 27.7 (0.4) 17.88 (0.56)
CaO 3.40 (0.27) 0.08 (0.01) 0.69 (0.02) 1.53 (0.16) 5.13 (1.05) 0.15 (0.01) 1.47 (0.06) 2.73 (0.13)
Na2O 0.73 (0.07) 0.06 (0.01) 0.25 (0.01) 0.06 (0.01) 1.51 (0.37) 0.10 (0.01) 0.44 (0.02) 0.09 (0.01)
K2O 0.12 (0.02) b.d.l. b.d.l. b.d.l. 0.27 (0.14) b.d.l. b.d.l. b.d.l.
P2O5 0.86 (0.05) b.d.l. b.d.l. 0.22 (0.06) 1.09 (0.33) 0.15 (0.14) b.d.l. 0.25 (0.03)
STE oxides 3.66 0.19 0.27 6.19 3.86 0.02 0.09 4.02
Total 96.56 98.73 98.82 101.56 98.08 101.14 101.12 100.01
Mg# 59.8 81.0 83.9 76.1 46.2 73.7 78.1 68.1
Phase abbreviations as in Table 2. Numbers in parentheses in column heading are number of spots analyzed, and columns give averaged
compositions for each phase. 1 r standard deviations appear beside each value. ‘‘STE oxides’’ denotes sum of oxides of trace elements (added
for use in partitioning study reported by Draper et al. [20]) present in each average phase composition. Contents below detection limits denoted
‘‘b.d.l.’’. Detection limits (wt.%): SiO2, 0.14; TiO2, 0.02; Al2O3, 0.02; FeO, 0.06; MgO, 0.04; CaO, 0.01; Na2O, 0.02; K2O, 0.01; P2O5, 0.03.

for olivine/liquid pairs in our experiments after the 2.4. Oxygen fugacity
method of Roeder and Emslie [25], which is in
excellent agreement with equilibrium KD values In solid media multi-anvil experiments, oxygen
expected at high pressure [26]. fugacity is buffered by the starting materials and the

Table 4
Electron microprobe analyses of f 5 GPa run products from natural Homestead
Silicates run AW4 Silicates run AW3
Liq(18) Ol(13) Opx(11) Liq(10) Ol(8) Opx(7) Gt(6)
SiO2 45.7 (0.5) 40.7 (0.2) 58.3 (0.3) 44.3 (2.1) 39.6 (0.2) 57.0 (0.4) 44.0 (0.3)
TiO2 0.58 (0.03) 0.01 (0.01) 0.01 (0.02) 0.26 (0.04) 0.01 (0.01) 0.02 (0.02) 0.14 (0.03)
Al2O3 3.81 (0.12) 0.12 (0.02) 0.88 (0.16) 3.87 (0.47) 0.15 (0.02) 2.21 (0.37) 19.51 (0.62)
FeO 20.54 (0.6) 12.44 (0.66) 6.55 (0.33) 21.90 (2.21) 19.60 (0.35) 9.71 (0.46) 10.51 (0.19)
MgO 24.52 (0.41) 48.10 (0.40) 34.62 (0.36) 22.99 (1.08) 42.85 (0.44) 29.94 (2.09) 22.13 (0.38)
MnO 0.49 (0.02) 0.23 (0.02) 0.20 (0.02) 0.52 (0.04) 0.34 (0.03) 0.32 (0.05) 0.50 (0.03)
CaO 3.15 (0.08) 0.10 (0.03) 0.52 (0.06) 3.69 (0.35) 0.13 (0.02) 1.75 (1.11) 2.87 (0.11)
Na2O 1.57 (0.10) 0.05 (0.01) 0.19 (0.03) 1.89 (0.18) 0.11 (0.01) 0.76 (0.39) 0.10 (0.02)
K2O 0.19 (0.02) b.d.l. b.d.l. 0.17 (0.03) b.d.l. b.d.l. b.d.l.
P2O5 0.13 (0.03) 0.01 (0.01) b.d.l. 0.24 (0.15) 0.02 (0.01) b.d.l. 0.06 (0.00)
Cr2O3 0.72 (0.04) 0.31 (0.04) 0.31 (0.03) 0.70 (0.09) 0.29 (0.03) 0.61 (0.11) 2.99 (0.19)
Total (wt.%) 100.9 102.0 101.5 100.5 103.1 102.3 102.8
Mg# 68.0 87.3 90.4 65.2 79.6 84.6 79.0

Quench metal run AW4 Quench metal run AW3

Si 0.05 (0.04) 0.01 (0.01)
P 0.06 (0.02) 0.01 (0.01)
Fe 77.14 (1.07) 75.23 (3.15)
S 10.96 (2.31) 14.82 (3.50)
Cr 0.13 (0.22) 0.02 (0.01)
Co 0.60 (0.02) 0.55 (0.02)
Ni 7.67 (1.33) 6.84 (0.97)
Total (wt.%) 96.62 97.50
 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429
Fig. 2. Backscattered electron image of a polished-section run product. Crystalline phases are garnet (Gt), low-calcium pyroxene (Opx), and
olivine (Ol). Lightest gray region with dendritic texture in the upper and lower center of the image consists of quenched crystals and glass. Black
regions at top and bottom of image are the graphite capsule.
sample container. Unfortunately, direct measurement
of oxygen fugacity is usually not feasible in melting
experiments such as those presented here. However, if
silicate liquid and Fe-metallic liquid coexist in the
experimental run products, an estimate of oxygen
fugacity (fO2) relative to the iron –wüstite (IW) buffer
can often be calculated (see, for example, [24,27]). Our
experimental products from the natural Homestead
starting materials contain both silicate and metal, thus,
we were able to calculate fO2 for runs AW3 and AW4
of 1.03 and 0.94 log units below the iron –wüstite
buffer, respectively. The synthetic starting material
represents only the silicate fraction of Homestead,
and hence is metal free. Therefore, the fO2 of these
experiments cannot be calculated relative to the IW
buffer. Nonetheless, the phase relations and the FeO
contents of silicate liquids and minerals in the synthetic
run products are nearly identical to the run products
from natural Homestead starting materials at a given
temperature and pressure (Tables 2 –4). This suggests
that the fO2 of the synthetic experiments is similar to
the natural Homestead experiments but slightly higher
than the IW buffer. We also believe that there is little or
no Fe3 + present in the silicate liquids since the olivine/
liquid KD mentioned above does not show anoma-
lously low values (i.e., KD < 0.20). The fact that our
421
experiments were run at conditions near the IW buffer
makes them relevant to the oxygen fugacity of the
Martian mantle and the SNC meteorites which recent
studies place near to or slightly higher than IW [28].
2.5. Analytical conditions
Run products were analyzed with a Cameca SX-
100 electron microprobe at the Johnson Space Center
operating at 20 keV accelerating potential and using
standards of natural and synthetic minerals and
glasses. Analytical conditions were dictated by our
requirements to obtain good trace element data for the
partitioning study of Draper et al. [20]. Mineral phases
were analyzed with a focused, 1-Am beam and
quenched melt was analyzed with a defocused beam
or rastered area (at least 20 Am in longest dimension
but as large as 50 Am when quenched melt areas were
sufficiently large). Initially (run numbers below 200,
Tables 2 and 3), major elements were counted for 20 s
on peak and 10 s on background with a beam current
of 30 nA, and trace elements were counted for 120 –
150 s on peak and 60 – 80 s on background with a
beam current of 200 nA. This was found to be
inefficient, however, as total time per analysis
exceeded 30 min. It was found, as well, that 60 s
422 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429
counting times on peak at 200 nA more than sufficed
to obtain adequate counts for the trace element anal-
yses. The analytical routine was therefore modified
(run numbers above 200) with more efficient assign-
ments of available spectrometers and use of 200 nA
beam current for all elements analyzed. In this con-
figuration, major elements (Si, Al, Fe, Mg, and Ca)
were counted for 6 s on peak and 3 s on background;
minor elements (K, Na, P, and Ti) were counted for
10 s on peak and 5 s on background; and trace
elements were counted for 60 s on peak and 30 s on
background. Several run products were analyzed un-
der both sets of conditions with statistically indistin-
guishable results. Run products of experiments AW3
and AW4, from natural Homestead starting material,
were analyzed with a JEOL 8200 electron microprobe
at the University of New Mexico. Silicates were
analyzed under conditions described above. Quench
metal domains were analyzed at 15 keV accelerating
potential with a 20-Am defocused beam. Fe and S were
counted for 20 s on peak and 10 s on background with
a beam current of 50 nA, with all other elements
counted for 90 s on peak and 30 s on background.
2.6. Experimental data
Table 2 lists run conditions for experiments carried
out at 4.7– 5.0 GPa. Tables 3 and 4 list compositions
of coexisting minerals and quenched melt in these
runs where we obtained a set of melt compositions
ranging from near solidus and to near liquidus temper-
atures. The experiments are of importance because
garnet coexists with olivine, low-Ca pyroxene, and
liquid in nine of these runs—three others at higher
temperatures demonstrate that garnet is consumed by
melting near the liquidus. Hence, the experiments
cover P – T conditions where the influence of garnet/
liquid element partitioning becomes significant in this
bulk composition. Now we focus on the constraints
these experiments place on the relationship between
Martian basalts and the mantle source region from
which they were originally derived.
3. Melt compositions at f5 GPa
Major element compositions of partial melts and
coexisting crystals in our experiments at 4.7– 5.0 GPa
follow very coherent trends as shown in Fig. 3. Low
degree melts, closest to the solidus temperature, are
characterized by high CaO/Al2O3 and low Mg#, while
high degree melts, near the liquidus, have composi-
tions that are similar to the starting composition. The
variation in melt Al2O3 and CaO content is strongly
influenced by the temperature effect on the stability of
garnet. For example, as temperature increases, the
amount of garnet dissolved in the melt increases,
and this is one of the main factors for producing the
Al2O3 versus CaO/Al2O3 and CaO versus CaO/Al2O3
liquid trends in Fig. 3. In the experiments where
garnet is present, the coexisting liquid has super-
chondritic CaO/Al2O3. In the experiments at high
degrees of melting, with only olivine and pyroxene
present, the liquid composition is approximately
chondritic with respect to these oxides.
The liquid trends for FeO versus Mg# and MgO
versus Mg# in Fig. 3 are caused by the temperature
effect on FeO – MgO partitioning between liquid and
the three crystalline phases. All phases show decreas-
ing FeO and increasing MgO (and Mg#) with increas-
ing temperature and degree of melting. FeO is
incompatible in all coexisting crystalline phases at
all temperatures, and this results in relatively high
FeO contents for the liquids, particularly at low
degrees of partial melting. It is noteworthy that the
bulk composition (synthetic Homestead) plots interior
to the liquid and crystalline phases in Fig. 3, indicat-
ing mass balance and further supporting our claim of a
close approach to equilibrium in these experiments.
4. Comparison with low-pressure partial melting
experiments
Bertka and Holloway [7] (hereafter BH94) per-
formed a series of melting experiments on the DW-
Mars composition at 1.5 GPa to explore the possibility
that shergottite parent magmas could be derived from
a shallow mantle or deep crustal source region in
Mars. Fig. 4 summarizes the melt compositions of
BH94 and compares them to our melt compositions
from f 5 GPa and to the composition of Mars parent
magmas that were discussed above and in Fig. 1.
BH94 noted that none of their partial melts possessed
a sufficiently high CaO/Al2O3 to match the shergottite
meteorites and some proposed Mars parent magmas.
 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429 423

Fig. 3. Major element compositions of phases coexisting in melting experiments of synthetic Homestead at 5 GPa. The trends shown by linear
regression through the data reflect compositional changes as melt fraction increases with temperature. High degree melts are characterized by
low CaO/Al2O3 and high Mg#. Low degree melts are characterized by high CaO/Al2O3 and low Mg#. The large diamond symbols are for the
synthetic Homestead starting material.

Fig. 4 confirms this conclusion for the Mars parent
magmas considered in this study, showing that all
Mars parent magmas have CaO/Al2O3>1 while all of
the BH94 partial melts have CaO/Al2O3 < 1. Indeed,
low temperature, low degree melts of BH94 have high
Al2O3 and slightly sub-chondritic CaO/Al2O3, while
their high temperature, high degree melts nearly
recover the chondritic Al2O3 and CaO/Al2O3 of the
starting composition. CaO/Al2O3 is either sub-chon-
dritic or nearly chondritic in all their melt composi-
tions because there is no crystalline phase present,
such as garnet, in which Al2O3 is strongly compatible
relative to liquid. On the contrary, at low degrees of
melting, the BH94 experiments contain olivine, low-
Ca pyroxene, and high-Ca pyroxene. The presence of
high-Ca pyroxene causes the liquid to have a sub-
chondritic CaO/Al2O3. When all of the high-Ca py-
roxene is consumed at higher degrees of melting, the
liquid is nearly chondritic and remains so with in-
creasing temperature up to and including the liquidus.
The constant liquid CaO/Al2O3 content at higher
degrees of melting is due to the fact that low-Ca
pyroxene and olivine are the only crystalline phases
coexisting with liquid; neither phase strongly frac-
tionates CaO from Al2O3.
Fig. 4 shows that our f 5 GPa liquid trend is
dramatically different from the 1.5 GPa liquids of
BH94. The liquids from experiments at f 5 GPa in
which garnet is present have low Al2O3 and super-
chondritic CaO/Al2O3 c 1.0 –1.7. Fig. 4 also shows
that the f 5 GPa liquid trend covers the entire CaO/
Al2O3 range of Mars parent magmas, which spans
values between 1.0 and 1.5. On the other hand, all of
our liquid compositions at f 5 GPa have Al2O3
contents in the range of approximately 3 –5 wt.%,
while Mars parent magmas have values that are much
424 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429

Fig. 4. Al2O3 versus CaO/Al2O3 (wt.%) diagram showing compositions of Mars mantle liquid compositions with various degrees of partial
melting at 1.5 and 5.0 GPa. The 1.5 GPa data are from Bertka and Holloway [7]. The 5 GPa data are from this study. Shown also are the
proposed Mars Parent Magmas described in Fig. 1 and the compositions of the Dreibus – Wänke Martian mantle (DW-Mars), and the synthetic
Homestead starting material (Syn. Homestead).

higher, ranging from approximately 6 –10 wt.%. From
the lower pressure data of BH94 and our higher
pressure data at f 5 GPa, we conclude that the
CaO/Al2O3 and Al2O3 content of Mars parent mag-
mas cannot be simultaneously derived from single
stage melting of a DW-Mars composition. It is,
however, likely that both CaO/Al2O3 and Al2O3 of
Mars parent magmas can be derived by two stages of
magmatism in a DW-Mars mantle, as described in the
following section.
5. Two-stage process required for CaO and Al2O3
Fig. 5 forms the basis for a possible two-stage
mechanism in which melting and fractionation in a
DW-Mars mantle produces the CaO/Al2O3, Al2O3
and CaO content range of Mars parent magmas. The
first stage is a partial melting event at a pressure of
f 5 GPa (f 425 km depth in Mars) in which
garnet, pyroxene, and olivine coexist with silicate
liquid. This stage corresponds to our experiments
having low to medium degrees of melting in which
quenched liquids have CaO/Al2O3 values between 1
and 1.5, covering the range of Mars parent magmas.
The physical setting of this partial melting could be
a rising diapir or plume that reaches and exceeds
the solidus temperature of the Martian mantle at
f 425 km. The second stage of this scenario occurs
after the melt rises to the shallow mantle or crustal
levels. At these lower pressures, olivine crystallizes
and sinks, after which the remaining fractionated
magma (Mars parent magma) is emplaced higher in
the crust to become the source for basaltic shergot-
tites. Olivine fractionation has the effect of increas-
ing the Al2O3 and CaO content to the desired range
for Mars parent magmas without further perturbing
the super-chondritic CaO/Al2O3 first acquired by par-
tial melting at f 5 GPa (arrow in Fig. 5). The timing of
the two stages is not constrained by the phase equi-
libria relations or the major element fractionations;
however, the order in which the stages occur prob-
ably is. For example, it is physically implausible to
subtract olivine first at low pressure in the crust and
then partially remelt the resulting olivine fractionate
at some great depth (f 425 km) in the Martian
interior.
Another possible mechanism is that the first stage
partial melting is a planet-wide event such as a
magma ocean that reaches or exceeds depths of
 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429 425

Fig. 5. CaO and Al2O3 versus CaO/Al2O3 (wt.%) diagram showing the trend of 5 GPa liquids (best fit line to bold circles) produced by melting
analog Mars mantle (synthetic Homestead, large diamonds) and proposed Mars parent magma compositions (open hexagons) described in Fig.
1. Liquids from intermediate degrees of melting at 5 GPa have CaO/Al2O3 that cover the range of Mars parent magmas (>1.0 and < 1.5).
Vertical arrows illustrate that olivine fractionation increases the liquid CaO and Al2O3 contents to the values of proposed Mars parent magmas.

425 km in the Martian interior. In this case, the
magma ocean liquid acquires super-chondritic CaO/
Al2O3 from equilibration with garnet, olivine, and
pyroxene at its base. The second stage of olivine
fractionation might occur after solidification of the
magma ocean in a remelted shallow-mantle or deep-
crustal parcel to form the source material for basaltic
shergottites. Alternatively, the second stage could be
a polybaric process within the magma ocean column
that proceeds simultaneously with stage one. Here,
liquidus olivine crystals from the upper reaches of
the magma ocean would sink to the bottom, enrich-
ing the liquid column in Al2O3 and CaO. Once
solidified, this upper layer of the mantle becomes
the source region for basaltic shergottites by later
episodes of shallow, low-pressure partial melting. As
before, it is not possible to distinguish between these
mechanisms based solely on our experimental
426 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429

results. Finally, it is well-established from isotopic
studies [29,30] that the shergottite source region has
been substantially ‘‘processed’’ from an assumed
initially chondritic composition. The sorts of mech-
anisms discussed here would constitute means by
which such ‘‘processing’’ might (at least partially)
take place.
6. The FeO content of the Martian mantle
Our experiments show that Homestead and DW-
Mars can produce the CaO/Al2O3, CaO, and Al2O3
values of Martian parent magmas by high-pressure
partial melting and a second stage of olivine fraction-
ation. Thus, the SNC ‘‘aluminum depletion enigma’’

Fig. 6. FeO and MgO versus Mg# diagram showing the trend of 5 GPa liquids (best fit line to bold circles) produced by melting analog Mars
mantle (synthetic Homestead, large black diamonds) and proposed Mars parent magma compositions (open hexagons) described in Fig. 1.
Liquids from all degrees of melting at 5 GPa have Mg# similar to those of proposed Mars parent magmas, but FeO contents of the 5 GPa liquids
are significantly higher. Arrows illustrate that olivine fractionation (f Fo77) drives the liquids to even higher FeO contents diverging from the
values of Mars parent magmas. In contrast, olivine fractionation drives the 5 GPa liquids to MgO contents that are similar to those of proposed
Mars parent magmas.
 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429 427

has an apparent explanation. However, our experi-
ments also show that partial melts of Homestead at
f 5 GPa are far too FeO-rich to match values
observed in SNCs and their calculated parent mag-
mas. Fig. 6 illustrates that our partial melts have FeO
contents ranging from approximately 20– 30 wt.%,
whereas proposed Martian parent magmas fall within
the range 14 –20 wt % FeO. This mismatch is not
remedied by a second stage of olivine fractionation,
which actually increases the FeO content of the liquid
to still higher values shown by the arrow in Fig. 6.
The MgO contents of Homestead partial melts at 5
GPa are also higher than are those of proposed
Martian parent magmas, but in this case, the mismatch
is not as pronounced as for FeO. The arrow in Fig. 6
showing the effect of olivine fractionation (f Fo77)
on MgO versus Mg# suggests a near match with
‘‘evolved’’ Martian parent magmas ‘‘Sm’’ and ‘‘Ch’’.

Fig. 7. FeO and MgO (wt.%) versus Mg# diagram showing the trend of average values for C, LL, L, and H chondrites (gray diamonds). H-
chondrites have higher Mg# and lower FeO contents than do the other chondrites shown. Thus, high-pressure liquids from partial melting of H-
chondrite may have lower FeO which could be a better match for Martian parent magmas. Peridotite KLB-1 [42], representative composition of
the Earth’s upper mantle, is shown for comparison (triangle with cross symbol).
428 C.B. Agee, D.S. Draper / Earth and Planetary Science Letters 224 (2004) 415–429
We see no obvious differentiation scenario that
produces the FeO content of Martian parent magmas
from Homestead or a DW-Mars composition at high
pressure. It may, however, be possible to derive
Martian parent magmas at high pressure from a
different bulk mantle composition with a lower
FeO content and thus higher Mg# than that of
DW-Mars or Homestead L5. The FeO content of
chondritic meteorites covers a very large range, from
27 to 30 wt.% in carbonaceous chondrites to virtu-
ally none in the silicate portion of enstatite chon-
drites [31]. We are aware that several studies (e.g.,
[32 – 34]) have emphasized the importance of the
Martian moment of inertia factor as a constraint
requiring a comparatively high-density mantle with
high FeO content such as DW-Mars. However, the
moment of inertia factor, regardless of how well it is
known, cannot at this time give us a unique solution
for Martian mantle composition without detailed
information (e.g., high-quality seismic velocity data)
on the internal structure and density distribution
within the Martian crust, mantle, and core. For
example, some calculations of FeO contents and
Mg#s for Martian mantle that have been proposed
make use of the moment of inertia factor and assume
a priori that the S content of the Martian core is 14
wt.%. This assumption is in turn based on accretion-
ary models for the terrestrial planets, such as Dreibus
and Wänke [35]. We believe these estimates of the S
content of the Martian core to be sufficiently uncer-
tain to allow for a slightly less Fe-rich Martian
mantle while still accommodating the measured
moment of inertia factor (see, for example, [36]).
A more detailed assessment of these interactions will
be presented in a subsequent contribution.
From these considerations, we believe that it is
desirable to explore other chondrite compositions as
possible alternative Mars mantle candidates. Fig. 7
shows that the silicate fraction of average H-chondrite
has a lower FeO content and a higher Mg# than does
DW-Mars, although it is not as Mg-rich and Fe-poor
as the Earth’s upper mantle. At present, no high-
pressure melting experiments on H-chondrite exist,
however, it is likely that partial melts from this
composition will have lower FeO than melts from
Homestead. Determination of whether these melts are
good matches for Martian parent magma composi-
tions must await future studies.
Acknowledgements
We thank Linda Elkins-Tanton and Kevin Righter
for insightful reviews that helped improve the
manuscript. This research was supported by the
NASA Cosmochemistry Program. [KF]
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