Lithos 91 (2006) 46 – 58

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A high-pressure experimental study on the evolution of

the silicic magmatism of the Main Ethiopian Rift
L. Caricchi a,⁎, P. Ulmer a , A. Peccerillo b
a
Institute for Mineralogy and Petrology, ETH-Zentrum, Zürich CH-8092, Switzerland
b
Dipartimento di Mineralogia e Petrografia, Università degli Studi di Perugia, Perugia 06100, Italy
Received 26 April 2005; accepted 13 March 2006
Available online 19 May 2006

Abstract

In this contribution we report the results of an experimental study that investigated equilibrium and fractional crystallization of
hydrous, transitional alkaline basalt at low oxygen fugacity, under lower to middle crustal conditions to constrain the generation of
subaluminous and peralkaline differentiation products that typically occur in rift systems. The experiments reveal that liquids
produced by equilibrium crystallization in the range 0.7–1 GPa cannot cross the subaluminous/peralkaline compositional divide. In
contrast, fractional crystallization experiments under isobaric and polybaric conditions approach closer the naturally observed trend
from subaluminous to evolved peralkaline products suggesting that polybaric differentiation starting at elevated pressures can
indeed lead to the transition from subaluminous to peralkaline derivative liquids. The presence of water in the parental magmas of
silicic derivative products is of prime importance for the fractionation equilibria as well as for the mobility of such magmas toward
shallow crustal levels.
We suggest that peralkaline magmas in rift environments are indicative for differentiation under relatively low oxygen
fugacity conditions in an extensional environment characterized by a high degree of crustal fracturing that allows rapid upward
migration of mafic parental magmas and formation of shallow magma reservoirs. Crystallization–differentiation of parental,
hydrous transitional alkaline basalt in such reservoirs is controlled by low pressure phase equilibria that typically evolve through
early saturation of anorthite-rich plagioclase and suppressed amphibole crystallization resulting in ‘low-alumina’, peralkaline
derivative liquids.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Rhyolites; Rift system; Equilibrium crystallization; Fractional crystallization; Peralkaline

1. Introduction Peralkaline magmas are only rarely present in colli-

Igneous products associated with continental break-
up and oceanic islands are typically characterized by
peralkaline trachytes and rhyolites representing the end
products of crystallization–differentiation of parental
basaltic magmas (Baker, 1975; Barberi et al., 1975).
⁎ Corresponding author. Tel.: +41 1 63 27 824; fax: +41 1 63 21 088.
E-mail address: luca.caricchi@erdw.ethz.ch (L. Caricchi).
0024-4937/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.lithos.2006.03.008
sional tectonic settings and are clearly restricted to
phases of local extension (MacDonald, 1974; Smith et
al., 1977). Geochemical, petrological and experimental
data identify protracted fractional crystallization of
alkaline basalts at low pressures (< 200 MPa) under
relatively low oxygen fugacity conditions (< FMQ) as a
potential process responsible for the generation of
peralkaline liquids (Scaillet and MacDonald, 2001,
2003; Nekvasil et al., 2004). In areas where large
 L. Caricchi et al. / Lithos 91 (2006) 46–58
volumes of differentiated peralkaline magmas coexist
with comparatively low volumes of basic products,
partial melting of crustal material, either represented by
underplated basic cumulates or by more acidic lower
crustal lithologies, has been invoked as the principal
process responsible for the generation of these peralka-
line magmas. However, so far, experimental studies,
including the present one, have not been able to
produce peralkaline liquids by partial melting of lower
crustal rocks.
The origin of peralkaline silicic magmas has attracted
considerable attention but the significance of the
tectonic environment for the occurrence of peralkaline
products has been studied in much less detail. In this
paper we focus on two principal observations: (1)
peralkaline products are invariably associated with an
extensional tectonic setting and (2) they either represent
the last stage of magmatic activity (Bohrson and Reid,
1997; Nekvasil et al., 2004) or form the principal
igneous products during a tectonically mature exten-
sional stage (e.g. Main Ethiopian Rift (MER); Barberi et
al., 1975; Chernet et al., 1998; Ayalew et al., 2002).
These observations strongly suggest an intimate rela-
tionship between extensional processes and the compo-
sition of silicic magmas (e.g. Mahood, 1984).
In this contribution we concentrate on the MER
where silicic magmas were erupted during the latest
stage of basaltic plateau formation (∼30 Ma; plateau
phase) and inside the Rift Valley (Plio-Quaternary;
intrarift phase). While the plateau phase rhyolites are
predominantly subaluminous and only sporadically
peralkaline (Ayalew et al., 2002), the intrarift phase
trachytes and rhyolites are peralkaline and represent the
overwhelming part of erupted magmas (Boccaletti et al.,
1995; Barberio et al., 1999). In both cases, geochemistry
strongly supports a genetic link between plateau
forming transitional basalts and silicic rocks (Barberio
et al., 1999; Chernet and Hart, 1999; Ayalew et al.,
2002; Peccerillo et al., 2003). It is, therefore, unlikely
that differences in parental magma compositions are
responsible for the variation in the chemistry and
characteristics of differentiated silicic magmas of the
plateau and intrarift phases. Moreover, isotope geo-
chemistry excludes partial melting of ancient crustal
material as a possible process generating peralkaline
products (Peccerillo et al., 1998, 2003).
2. Volcanological evolution of the Ethiopian Rift
The first magmatic activity in the MER (30 Ma,
Chernet et al., 1998; Ukstin et al., 2002) was marked by
voluminous eruptions of tholeiitic to transitional
47
alkaline basalts (3.5 × 105 km3, Mohr, 1983) over a
very short period (1–2 Ma, Hofmann et al., 1997). Only
during the last stage of this phase (plateau phase) limited
volumes of silicic magmas were emplaced by (probable)
fissure eruptions (Ayalew et al., 2002). Trachytes and
rhyolites erupted during this magmatic stage were
mainly subaluminous with only very subordinate
peralkaline varieties. During the intermediate phase
(8 Ma, Chernet et al., 1998), transitional between
plateau formation and rift valley opening, several shield
volcanoes erupted transitional to Na-alkaline basalts and
trachytes. In the Plio-Quaternary (Chernet et al., 1998)
magmatic activity focused along a structure of crustal
weakness (Wonji Fault Belt) in the axial portion of the
rift valley. During this phase, which represents the
waning stage of regional magmatic activity, several
central volcanoes erupted considerable amounts of
peralkaline trachytes and rhyolites. In contrast, the
emission of basic magmas was limited to isolated scoria
cones.
The following characteristics distinguish the silicic
magmatism occurring at the end of the plateau phase
from the igneous products that erupted during the
intrarift phase:
▪ During Oligocene, silicic magmas represent a minor
volume of the erupted products and were emplaced at
the end of the plateau forming magmatic phase. The
activity inside the rift valley is dominated by silicic
(trachytes and rhyolites) melts.
▪ Evolved magmas associated with plateau basalts are
subaluminous, mildly alkaline and only rarely
peralkaline, whereas silicic magmas characterizing
the Plio-Quaternary activity inside the rift are
predominantly peralkaline.
▪ The emplacement mechanism of silicic magmas
changed from fissural (plateau phase) to caldera-
forming eruptions (intrarift phase).
▪ The oldest silicic products contain amphibole
phenocrysts, whereas trachytes and rhyolites that
cover the rift valley floor only contain amphibole
microlites in the matrix.
▪ The presence of intrusive bodies associated with the
volcanoes that erupted the peralkaline products
(Mahatsente et al., 1999) testifies to the presence of
shallow reservoirs during the last stages of domi-
nantly silicic magmatic activity in the MER.
3. Experimental strategy and technique
The majority of experiments reported here are
equilibrium crystallization (EC) experiments on a
48 L. Caricchi et al. / Lithos 91 (2006) 46–58

transitional basaltic composition (AA1, Table 1) content was kept constant in the starting material
selected on the basis of geochemical, petrologic and (1000 ppm) during fractionation because F-content of
volcanologic constraints that clearly point to transitional amphibole and melt were not well constrained (large
basalts as potential parental magmas to produce errors).
derivative silicic magmas of mildly alkaline, subalumi- The different starting materials (Table 1) containing
nous to peralkaline affinity (Barberi et al., 1975; Deniel 4, 2, and 2.98 wt.% H2O were obtained by mixing a total
et al., 1994; Mungall and Martin, 1995; Civetta et al., of 4 g of oxides, hydroxides, carbonates and minerals in
1998; Peccerillo et al., 2003). Most experiments reported appropriate proportions (SiO2, TiO2, Al(OH)3, AlOOH,
here have been performed under hydrous conditions with CaCO3, Fe2SiO4, Na2SiO3, KAlSi3O8, Al2O3, MnO,
4 wt.% initial H2O. The presence of significant amounts CaHPO4, CaF2). AlOOH, Al(OH)3 and Al2O3 were
of H2O in the magmas parental to silicic derivatives is used to balance accurately the H2O and Al2O3 contents
clearly indicated by the caldera-forming highly explo- of the starting materials. SiO2, TiO2, CaCO3, MgO were
sive character of the Plio-Quaternary eruptions. fired for 4 h at 1000 °C to decarbonize CaCO3 and to
An additional EC experiment was performed at drive off adsorbed water; the fired powders were
0.7 GPa to test the effect of lower water content of the allowed to cool in a dessicator under vacuum to avoid
starting material (LCS2, 2 wt.%) on the residual melt water and CO2 absorption. After cooling the loss on
compositions. Additionally, we conducted two more ignition was monitored to control removal of all CO2
experiments at 0.7 and 0.5 GPa starting from the that was bound in calcium carbonate. All other
residual melt composition of run LCS2, to simulate components were stored at 220 °C, except the
isobaric and polybaric fractional crystallization (FC). In alumina-hydroxides that were kept at 110 °C, prior to
this approach the melt phase of the equilibrium weighing and mixing. Powders were homogenized in an
experiment (LCS2) became the new starting material agate mortar under ethanol, dried and then milled for
for the experiments at lower temperature (a detailed 15 min in an agate ball-grinder to produce a highly
description of the method is provided by Villiger et al., reactive (fine grained) starting material.
2004). The H2O-content of the starting material for the All experiments reported in Table 2 were carried out
FC experiments was calculated using the phase propor- in an end-loaded piston cylinder apparatus (Boyd and
tions obtained by the least square regression of run England, 1960) in the pressure–temperature range 0.5 to
LCS2. The amount of water contained in amphibole was 1 GPa and 950 to 1100 °C. The finely ground starting
taken into account for the calculations. The Fluorine material was loaded into graphite crucibles sealed by
arc-welding into Pt-capsules of 3 mm OD. Graphite
capsules combined with relatively high H2O-fugacity
Table 1 impose relatively low oxygen fugacity conditions on the
Starting compositions
experimental charge, about 1 log unit below the
AA1 SAA1 SAA2 FCS1 graphite–CO–CO2 equilibrium (Ulmer and Luth,
SiO2 50.01 48.51 49.51 52.07 1991) and have the additional advantage of avoiding
TiO2 1.91 1.85 1.89 2.12 iron-loss during the experiment. These double-capsules
Al2O3 16.10 15.62 15.94 16.92
were run in NaCl/Pyrex/BN assemblies. A friction
FeO 5.19 9.63 9.83 8.67
Fe2O3 5.26 – – – correction of − 3% was applied for this assemblage,
MnO 0.17 0.16 0.17 0.22 based on pressure calibrations using the fayalite +
MgO 7.31 7.09 7.24 3.42 quartz= orthoferrosilite equilibrium (Bohlen et al., 1980).
CaO 8.16 7.92 8.08 6.67 This value for the friction correction is identical with
Na2O 3.44 3.34 3.41 4.01
the value reported by McDade et al. (2002) for similar
K2O 1.50 1.46 1.49 2.22
P2O5 0.33 0.32 0.33 0.60 assemblies.
F – 0.10 0.10 0.10 Temperature was measured by B-type (Pt6Rh94–
H2O 0.60 4.00 2.00 2.98 Pt30Rh70) thermocouples calibrated against the melting
Total 99.98 100.00 100.00 100.00 point of gold at 1 bar. No correction was made for the
AA1 represents a natural, transitional alkaline basalt composition of pressure effects on e.m.f.
the plateau series analyzed by XRF; H2O-content represents loss on
ignition. SAA1 and SAA2 are synthetic equivalents containing 4 and 4. Analytical technique
2 wt.% H2O respectively. In the synthetic mixtures all iron was
considered ferrous and added as fayalite. FCS1 is the starting material
used for fractional crystallization experiments and corresponds to the All experimental charges were analyzed by a JEOL
liquid phase of run LCS2 (0.7 GPa and 1050 °C). JXA-8200 electron microprobe. The analytical
Table 2
Experimental conditions, phase proportions and analytical results of the run products
Run P T ΣR2 Run duration Phase SiO2 TiO2 Al2O3 FeO MnO MgO CaO Na2O K2O P2O5 Total
(GPa) (°C) (h) [wt.%]
LC13 0.7 950 0.46 50 amph [58] 41.74 (0.04) 3.64 (0.31) 11.41 (0.01) 14.91 (2.10) 0.19 (0.01) 12.11 (1.26) 9.79 (0.14) 2.56 (0.08) 0.68 (0.02) 0.04 (0.01) 97.05
plg [26] 60.16 (2.12) 0.07 (0.05) 24.52 (0.52) 0.71 (0.29) 0.01 (0.01) 0.14 (0.06) 6.71 (1.51) 6.03 (1.11) 0.85 (0.05) 0.03 (0.04) 99.23
melt [16] 64.06 (0.05) 0.54 (0.03) 18.45 (0.32) 4.81 (0.11) 0.12 (0.03) 1.02 (0.08) 3.20 (0.03) 4.03 (0.18) 3.49 (0.07) 0.28 (0.02) 100.00 (90.92)
LC11 0.7 1000 0.02 48 amph [27] 41.08 (0.68) 3.66 (0.15) 13.31 (0.77) 12.07 (0.37) 0.10 (0.02) 12.98 (0.32) 10.70 (0.48) 2.31 (0.07) 0.71 (0.06) 0.04 (0.02) 96.95
cpx [6] 50.86 (0.56) 0.84 (0.09) 3.97 (0.63) 11.13 (0.85) 0.19 (0.03) 13.99 (0.64) 17.39 (0.62) 0.49 (0.10) 0.11 (0.07) 0.04 (0.03) 99.01
ol [3] 36.47 (0.19) 0.07 (0.04) 0.11 (0.06) 30.91 (1.05) 0.27 (0.02) 32.20 (0.86) 0.29 (0.08) 0.03 (0.02) 0.02 (0.01) 0.05 (0.02) 100.42
plg [6] 55.15 (0.33) 0.08 (0.02) 27.36 (0.25) 0.58 (0.05) 0.01 (0.01) 0.12 (0.03) 10.43 (0.19) 4.78 (0.12) 0.31 (0.02) 0.03 (0.01) 98.87
melt [57] 54.94 (0.46) 1.48 (0.09) 18.23 (0.29) 9.17 (0.18) 0.12 (0.02) 3.67 (0.28) 7.00 (0.07) 3.32 (0.31) 1.59 (0.17) 0.45 (0.05) 100.00 (90.06)
LC10 0.7 1050 0.01 48 amph [4] 40.11 (0.66) 5.47 (0.17) 14.56 (0.64) 10.49 (0.12) 0.15 (0.02) 13.25 (0.38) 11.12 (0.20) 2.69 (0.09) 0.76 (0.07) 0.00 (0.00) 98.58
cpx [9] 49.30 (0.52) 1.62 (0.08) 5.91 (0.28) 8.27 (0.24) 0.24 (0.03) 14.26 (0.29) 19.98 (0.11) 0.53 (0.04) 0.05 (0.01) 0.03 (0.02) 100.20
ol [10] 36.33 (0.92) 0.06 (0.03) 0.02 (0.02) 29.37 (0.81) 0.42 (0.04) 33.31 (0.60) 0.28 (0.03) 0.02 (0.02) 0.01 (0.01) 0.03 (0.02) 99.87
plg [12] 52.94 (0.34) 0.09 (0.02) 29.50 (0.29) 0.48 (0.03) 0.01 (0.01) 0.06 (0.02) 12.91 (0.36) 4.45 (0.16) 0.28 (0.03) 0.02 (0.02) 100.74
melt [65] 53.15 (0.32) 2.21 (0.07) 17.72 (0.22) 9.16 (0.09) 0.23 (0.04) 3.31 (0.99) 6.97 (0.09) 4.56 (0.12) 2.17 (0.05) 0.49 (0.04) 100.00 (96.25)

L. Caricchi et al. / Lithos 91 (2006) 46–58

LC12 0.7 1100 0.08 48 cpx [9] 50.76 (0.21) 1.39 (0.01) 6.05 (0.03) 7.92 (0.03) 0.08 (0.00) 14.89 (0.06) 18.93 (0.08) 0.50 (0.00) 0.04 (0.00) 0.00 (0.00) 100.56
ol [6] 38.75 (0.01) 0.04 (0.01) 0.00 (0.00) 24.77 (0.00) 0.32 (0.52) 37.22 (0.01) 0.23 (0.42) 0.00 (0.00) 0.00 (0.00) 0.00 (0.00) 101.33
plg [4] 53.51 (0.15) 0.07 (0.00) 31.00 (0.06) 0.36 (0.06) 0.00 (0.00) 0.13 (0.01) 12.21 (0.18) 4.32 (0.01) 0.26 (0.03) 0.00 (0.00) 101.85
melt [80] 51.68 (0.04) 2.25 (0.01) 18.02 (0.25) 9.81 (0.04) 0.16 (0.08) 4.66 (0.07) 7.54 (0.19) 3.87 (0.11) 1.59 (0.07) 0.16 (0.07) 100.00 (97.45)
LC6 1 950 0.58 64.5 amph [57] 41.40 (0.27) 2.63 (0.43) 13.71 (0.48) 14.21 (1.02) 0.22 (0.04) 11.52 (0.60) 9.98 (0.28) 2.47 (0.08) 0.79 (0.04) 0.04 (0.01) 96.97
melt [43] 61.41 (0.52) 0.68 (0.07) 19.74 (0.33) 5.24 (0.546) 0.10 (0.05) 1.05 (0.28) 4.63 (0.13) 4.35 (0.16) 2.20 (0.09) 0.71 (0.56) 100.00 (87.60)
LC5 1 1000 0.10 48 amph [29] 41.05 (0.67) 3.03 (0.28) 13.93 (0.92) 11.76 (1.22) 0.11 (0.02) 13.30 (0.67) 10.08 (0.61) 2.38 (0.07) 0.77 (0.07) 0.03 (0.02) 96.45
cpx [4] 50.77 (0.40) 0.70 (0.06) 4.09 (0.45) 10.16 (0.44) 0.19 (0.01) 14.39 (0.44) 18.16 (0.43) 0.47 (0.07) 0.09 (0.04) 0.03 (0.01) 99.04
ol [1] 36.57 (0.10) 0.08 (0.02) 0.18 (0.03) 29.07 (0.08) 0.25 (0.04) 33.58 (0.15) 0.24 (0.03) 0.03 (0.01) 0.02 (0.02) 0.07 (0.03) 100.08
melt [65] 54.94 (0.04) 1.48 (0.09) 18.23 (0.29) 9.17 (0.18) 0.12 (0.02) 3.67 (0.28) 7.00 (0.07) 3.32 (0.31) 1.60 (0.17) 0.46 (0.05) 100.00 (87.76)
LC7 1 1050 0.03 48 cpx [4] 50.67 (0.50) 1.07 (0.13) 4.49 (0.87) 8.02 (1.2) 0.13 (0.03) 15.46 (0.38) 19.17 (1.03) 0.57 (0.07) 0.07 (0.04) 0.02 (0.02) 99.67
ol [6] 37.89 (0.18) 0.07 (0.01) 0.14 (0.03) 25.05 (0.85) 0.22 (0.01) 38.02 (0.61) 0.28 (0.02) 0.04 (0.02) 0.02 (0.01) 0.02 (0.02) 101.75
melt [90] 51.40 (0.36) 2.10 (0.07) 17.78 (0.19) 9.34 (0.14) 0.11 (0.03) 5.14 (0.15) 8.34 (0.16) 3.86 (0.07) 1.57 (0.04) 0.37 (0.06) 100.00 (98.88)
LC8 1 1100 0.01 44 cpx [11] 49.38 (0.69) 1.11 (0.13) 6.07 (0.71) 8.85 (0.67) 0.28 (0.05) 15.49 (0.67) 17.12 (0.81) 0.55 (0.04) 0.02 (0.01) 0.00 (0.01) 98.88
ol [4] 37.57 (0.18) 0.06 (0.03) 0.03 (0.02) 24.67 (0.34) 0.32 (0.02) 37.48 (0.42) 0.22 (0.02) 0.03 (0.04) 0.01 (0.01) 0.04 (0.01) 100.41
melt [85] 51.35 (0.36) 2.12 (0.09) 18.40 (0.28) 9.52 (0.16) 0.20 (0.03) 4.86 (0.14) 7.42 (0.11) 3.93 (0.10) 1.78 (0.05) 0.41 (0.06) 100.00 (92.96)
LCS2 0.7 1050 0.10 48 amph [8] 41.04 (0.88) 4.95 (0.44) 13.37 (0.64) 9.54 (0.25) 0.22 (0.04) 14.16 (0.38) 10.80 (0.29) 2.69 (0.12) 0.78 (0.09) 0.05 (0.03) 97.60
ol [11] 37.40 (0.70) 0.08 (0.09) 0.15 (0.35) 28.00 (0.67) 0.54 (0.04) 33.62 (1.15) 0.61 (0.89) 0.04 (0.06) 0.01 (0.01) 0.05 (0.03) 100.50
cpx [6] 51.05 (0.26) 1.07 (0.15) 3.70 (0.44) 10.60 (0.80) 0.38 (0.07) 14.52 (0.53) 18.78 (1.49) 0.54 (0.14) 0.05 (0.01) 0.07 (0.04) 100.77
plg [13] 53.18 (0.28) 0.07 (0.01) 28.89 (0.34) 0.20 (0.06) 0.02 (0.01) 0.06 (0.01) 12.35 (0.14) 4.65 (0.17) 0.32 (0.01) 0.02 (0.02) 99.76
melt [62] 53.72 (0.33) 2.19 (0.07) 17.46 (0.36) 8.95 (0.34) 0.23 (0.06) 3.53 (0.06) 6.88 (0.08) 4.13 (0.14) 2.29 (0.08) 0.61 (0.14) 100.00 (96.03)
LCS2F7 0.7 970 0.29 48 amph [28] 41.33 (0.85) 3.88 (0.27) 11.93 (0.81) 15.56 (0.37) 0.20 (0.02) 11.05 (0.46) 10.47 (0.51) 2.41 (0.16) 0.94 (0.08) 0.02 (0.01) 97.80
plg [19] 57.24 (1.11) 0.11 (0.11) 26.34 (1.48) 0.66 (0.33) 0.01 (0.01) 0.14 (0.19) 9.33 (1.03) 5.57 (0.53) 0.55 (0.14) 0.06 (0.08) 100.00
ilm [1] 0.25 (0.16) 52.00 (0.47) 0.40 (0.12) 42.36 (0.57) 0.52 (0.02) 3.04 (0.17) 0.16 (0.02) 0.06 (0.02) 0.05 (0.02) 0.00 (0.00) 98.85
melt [52] 61.05 (0.16) 0.90 (0.06) 17.32 (0.20) 7.01 (0.07) 0.13 (0.02) 1.20 (0.05) 4.27 (0.05) 4.41 (0.19) 3.38 (0.05) 0.32 (0.02) 100.00 (94.25)
LCS2F5 0.5 950 0.44 48 amph [10] 42.09 (0.66) 3.83 (0.23) 10.89 (0.65) 15.24 (0.38) 0.21 (0.02) 11.79 (0.48) 10.09 (0.28) 2.71 (0.08) 0.76 (0.07) 0.05 (0.03) 97.66
ol [6] 34.07 (0.30) 0.08 (0.03) 0.19 (0.08) 44.37 (0.35) 0.67 (0.02) 21.08 (0.21) 0.35 (0.05) 0.07 (0.06) 0.04 (0.02) 0.13 (0.04) 101.06
cpx [5] 50.41 (0.60) 0.76 (0.07) 2.23 (0.39) 14.64 (0.99) 0.35 (0.06) 12.28 (0.70) 17.98 (0.44) 0.48 (0.08) 0.09 (0.02) 0.05 (0.04) 99.26
plg [35] 55.93 (1.11) 0.09 (0.02) 26.25 (0.82) 0.45 (0.02) 0.01 (0.01) 0.00 (0.00) 9.41 (0.85) 5.86 (0.45) 0.49 (0.08) 0.02 (0.01) 98.51
ilm [3] 0.36 (0.04) 51.98 (0.25) 0.30 (0.03) 42.13 (0.21) 0.56 (0.04) 3.21 (0.03) 0.22 (0.06) 0.07 (0.02) 0.06 (0.01) 0.00 (0.00) 98.89
melt [41] 61.94 (0.36) 0.77 (0.05) 17.06 (0.32) 6.31 (0.13) 0.13 (0.02) 1.11 (0.05) 3.77 (0.08) 5.07 (0.13) 3.53 (0.09) 0.29 (0.05) 100.00 (93.34)
Abbreviations: amph = amphibole, cpx = clinopyroxene, ol = olivine, plg = plagioclase, ilm = ilmenite, melt = quenched glass. Melt compositions are recalculated to 100 wt.% volatile-free (in parenthesis the actual value of the
totals from microprobe analyses). The numbers in square brackets in the column “Phase” indicate modal phase abundances (in wt.%) calculated by linear least square regression analysis. ΣR2 is the sum of the squares of the

49
residuals of the least square regression calculation. Units in parentheses for single oxides indicate standard errors (2σ) from average analysis.
50 L. Caricchi et al. / Lithos 91 (2006) 46–58
conditions for analysis of the mineral phases were 15 kV
acceleration voltage and 20 nA beam current. For the
melt phase the current was lowered to 7 nA and a
defocused beam was employed (10–20 μm, depending
on the size of the melt pools). Sodium and potassium
were analyzed first in order to decrease volatilization
effects.
5. Experimental results
The experimental run products resulted in subhedral
crystals and melt quenched to glass. Homogeneous
distribution of phases, absence of zoning in mineral
phases and low sums of residuals of the least squares
regression analyses (ΣR2 < 0.5, only run LC6 exhibits a
value of ΣR2 equal to 0.58; Table 2) indicate close
attainment of equilibrium in the charges. This is further
supported by experiments that contain olivine: we
computed the Fe+ 2–Mg partition coefficients between
olivine and melt, and, within error, they are in agreement
with Kd-values for basaltic compositions at pressure
between 0.5 and 1 GPa by Ulmer (1989; Fig. 1).
The following discussion of the experimental results
first presents a description of the solid assemblages
observed in the equilibrium and fractional crystalliza-
tion experiments, followed by the presentation of the
evolutionary trends of the residual melt compositions
produced via EC and FC.
Mineral assemblages and the relative phase propor-
tions for the EC and FC experiments are listed in Table 2
and illustrated in Fig. 2.
At 1 GPa olivine and clinopyroxene are the liquidus
phases at 1100 °C. Experiment LC7 (1 GPa, 1050 °C)
Fig. 1. Fe–Mg partition coefficients between olivine and melt as a
function of temperature (°C). Kd-values determined in this work agree
within error with the values of Ulmer (1989) for basaltic liquids that
are indicated by the grey field; this supports close attainment of
equilibrium in our experiments.
results a higher melt fraction than experiment LC8
(1 GPa, 1100 °C). This is most probably due to loss of
small amounts of water during the higher temperature
experiment (LC8) or hydrogen diffusion into the capsule
during the lower temperature experiment (LC7) that
reduced the oxygen fugacity and increased the water
content to reach equilibrium of the water speciation
reaction.
Olivine disappears from the mineral assemblage
between 1050 and 1000 °C while clinopyroxene is
stable down to 1000 °C where it is in equilibrium with
approximately 30 wt.% amphibole. At 950 °C clinopyr-
oxene is not longer stable, the amount of amphibole
increases to 53 wt.% whereas melt decreases from
65 wt.% at 1000 °C to 47 wt.%. Phase assemblages and
mineral proportions are consistent with peritectic
relationships of olivine, cpx, and melt forming amphi-
bole; plagioclase is not part of the stable mineral
assemblage down to 950 °C.
At 0.7 GPa plagioclase appears in the liquidus
assemblage in coexistence with olivine and clinopyrox-
ene at 1100 °C. The relative proportion of plagioclase
increases at 1050 °C and then slightly decreases to
1000 °C and increases again to reach 26 wt.% at 950 °C.
The amount of melt decreases continuously from 80 to
16 wt.% between 1100 and 950 °C. Amphibole appears
at 1050 °C and constantly increases from ∼5.5 to 58 wt.
% at 950 °C. The decrease of the modal proportion of
plagioclase between 1050 and 1000 °C is attributed to a
peritectic reaction forming amphibole that involves
olivine, cpx and plagioclase followed by cotectic
precipitation of plagioclase and amphibole at lower
temperature.
The relative phase proportions of LCS2 (0.7 GPa,
1050 °C and 2 wt.% H2O) are only slightly different
with respect to the experiment performed at the same
pressure–temperature conditions containing 4 wt.%
water. In particular, melt and clinopyroxene contents
decrease while amphibole, olivine and plagioclase
contents increase.
During FC at constant pressure starting from the melt
in equilibrium in LCS2 at 0.7 GPa and decreasing
temperature to 970 °C olivine and clinopyroxene
disappear at the expense of extensive amphibole and
moderate plagioclase crystallization. Experiment
LCFC5 simulated polybaric FC from 0.7 to 0.5 GPa
and 1050 to 950 °C. In this case, olivine and
clinopyroxene remain stable phenocryst phases but
their abundances decrease. In contrast to isobaric FC,
decreasing pressure results in strongly increasing
plagioclase abundances and nearly constant amphibole
proportions (Fig. 2). In EC experiments at 0.7 GPa,
 L. Caricchi et al. / Lithos 91 (2006) 46–58 51

Fig. 2. Relative phase proportions (in wt.%) of experimental charges calculated by the least square regression analysis. Plagioclase stability increases
with decreasing pressure. Equilibrium crystallization at 0.7 GPa results in a larger increase of amphibole between 1050 and 950 °C than polybaric
fractional crystallization that produces much higher modal proportions of plagioclase instead.

amphibole contents increase much more rapidly than
plagioclase abundances with decreasing temperature.
Ilmenite forms part of the solid assemblage in the FC
experiments.
Fig. 3 illustrates the variation of major element
compositions of melts as a function of temperature.
The SiO2, Na2O and K2O contents of the liquids
increase with decreasing temperature while TiO2,
MgO, CaO and FeO follow an opposite evolutionary
trend. Al2O3 does not vary substantially during EC at
0.7 GPa while it increases by more than 1 wt.% at
1 GPa between 1000 and 950 °C. The residual melt
composition produced from the starting material
containing only 2 wt.% H2O (LCS2) is comparable
52 L. Caricchi et al. / Lithos 91 (2006) 46–58

Fig. 3. Variations of major element compositions of experimentally produced liquids (quenched glasses) as a function of temperature (°C) at 0.5, 0.7
and 1.0 GPa for equilibrium and fractional crystallization.

with the melt obtained at the same pressure and
temperature condition with 4 wt.% water. Fractional
crystallization starting from the LCS2 melt composi-
tion at a constant pressure of 0.7 GPa (LCS2F7) or
coupled with pressure decrease to 0.5 GPa (LCS2F5)
results in melt compositions that contain higher FeO
and Na2O and lower Al2O3 contents with respect to
equilibrium crystallization consistent with prolonged
olivine and cpx crystallization and increased modal
amounts of plagioclase.
Fig. 4A and B summarize the effects of various
liquidus phases on the liquid lines of descent for
equilibrium and fractional crystallization respectively.
The variation of Al2O3, FeO and Na2O + K2O
 L. Caricchi et al. / Lithos 91 (2006) 46–58 53

contents of minerals and melts are plotted against
SiO2 that monotonically increases with increasing
differentiation.
Decreasing temperature in the equilibrium crystalli-
zation experiments leads to the crystallization of
massive amounts of amphibole below 1000 °C at
1 GPa and 1050 °C at 0.7 GPa that exerts the dominant
control on the evolution of the liquid phase (Fig. 4A).
The only appreciable difference between equilibrium
crystallization at 1 and 0.7 GPa is the presence of
plagioclase at lower pressure that has significant effect
on the extent of alumina increase with increasing
differentiation (Figs. 3 and 4A).
The small differences in melt composition pro-
duced by the decrease of the initial water content in
the starting material from 4 to 2 wt.% (lower Al2O3,
higher K2O and lower Na2O; Fig. 3) at the same
pressure and temperature conditions (LC10 and LCS2
respectively) are consistent with the slightly higher
plagioclase content in LCS2. In fact, mineral com-
positions in the two runs are identical within error
(Table 2).

Fig. 4. Al2O3, FeO and Na2O + K2O versus SiO2 concentrations (in wt.%) of solid and liquid phases. A. Results at 0.7 and 1.0 GPa for the equilibrium
crystallization experiments. At both pressures, amphibole is the principal phase controlling the compositional evolution of differentiated melts as their
trajectories are pointing straight away from amphibole compositions. Presence of plagioclase at 0.7 GPa results in less pronounced increase of
alumina in the residual melt at 950 °C. B. Results at 0.7 and 0.5 GPa for fractional crystallization. The lack of alumina increase and the moderate
decrease of FeO of the evolved liquids indicate that both, amphibole and plagioclase control the evolution of the Al2O3, FeO and Na2O + K2O
contents of the residual melts.
54 L. Caricchi et al. / Lithos 91 (2006) 46–58

Fig. 4 (continued).

As mentioned above, fractional crystallization pri-
marily affects the relative proportions of amphibole and
plagioclase that crystallize in the temperature interval
1000 to 950 °C and results in considerably different
derivative liquids (higher Na2O, K2O and lower Al2O3)
with respect to equilibrium crystallization. The effect of
fractional crystallization is even more pronounced under
polybaric conditions (LCS2F5), where the preference for
plagioclase over amphibole results in a slightly stronger
decrease of the alumina and iron contents of the
derivative melt (Fig. 4B).
Fig. 5 shows the variation of the Al-content of
plagioclase as a function of temperature that varies
linearly for the equilibrium crystallization experiments.
The plagioclases that are stable in the FC experiments
exhibit higher alumina and hence anorthite contents
than the plagioclases stable at the same temperature in
the EC experiments. This is most probably due to the
much lower amphibole contents in the FC runs respect
to the EC run at comparable temperature conditions.
Amphibole accommodates rather large amounts of
CaO relative to Na2O (9.8–10.5 and 2.4–2.7 wt.%
respectively); therefore larger modal abundance of
amphibole in the EC runs leads to effective depletion
of CaO in the melt phase and, consequently, to the
crystallization of a more albitic plagioclase compared
 L. Caricchi et al. / Lithos 91 (2006) 46–58 55

6. Comparison of the experimental melts with

natural rock compositions

The natural rock data of the Main Ethiopian Rift were

Fig. 5. Al2O3 contents of plagioclases as a function of temperature (°C)
in equilibrium and fractional crystallization experiments. Alumina
contents increase linearly with temperature. Plagioclases from
fractional crystallization experiments are shifted to higher Al2O3
(anorthite) contents.
to the FC experiments where the lower modal
abundance of amphibole results in higher CaO contents
in the melt phase and hence higher anorthite contents
of the plagioclase.
compiled from the following sources: plateau interme-
diate to acid rocks (Ayalew et al., 2002) and Quaternary
extrusive and intrusive products (Peccerillo et al., 2003).
The major element concentrations of natural rock
samples of the Oligo-Miocene and Plio-Quaternary
phases imply differences in major element chemistry of
their felsic products. Diagrams of Al2O3, FeO, and
Na2O against SiO2 (Fig. 6) clearly reveal distinct
trends for the high SiO2, differentiated products of the
different stages of rifting evolution. Evolved rocks of
the Oligo-Miocene magmatic phase invariably contain
higher Al2O3 and lower FeO and Na2O contents, at the
same SiO2-content, than the Plio-Quaternary trachytes
and rhyolites. Divergence of the two trends starts at
approximately 60 wt.% SiO2; pronounced decrease of
Al2O3 at basically constant FeO concentrations
characterizes the trend towards the most silica-rich,

Fig. 6. Comparison between experimentally produced liquid and natural rock compositions. Differentiation of basaltic magmas at relatively high-
pressure (indicated by the arrow labeled EC) drives residual melts toward subaluminous compositions that are typical for the ignimbrites of the
plateau phase. Fractional crystallization, in particular at lower pressure (indicated by the arrow labeled FC), tends towards alumina-poor, peralkaline
differentiates which form the bulk of the rocks erupted during the intrarift phase. The difference in chemical evolution of the two trends is related to
amphibole-dominated crystallization for the plateau phase versus plagioclase-dominated crystallization for the intrarift products.
56 L. Caricchi et al. / Lithos 91 (2006) 46–58
peralkaline Quaternary products. Dominant plagioclase
crystallization can easily account for this geochemical
trend. In contrast, the plateau ignimbrites show a
continuous decrease in FeO content and an evolution
towards higher Al2O3 values, with increasing differ-
entiation, compared with the intrarift peralkaline
pyroclastic products suggesting less important plagio-
clase crystallization during their late-stage fraction-
ation. Enhanced plagioclase crystallization and lack or
delayed amphibole crystallization are typical features
of low(er) pressure magma evolution (e.g. Nekvasil et
al., 2004) pointing to shallower magma reservoirs
during the later, advanced, more mature stages of rift
evolution.
Equilibrium crystallization experiments produce melt
compositions that invariably have higher alumina-
contents than the natural rocks at both pressures
investigated (Fig. 6) but their evolution points toward
the plateau series compositions with regard to iron,
sodium and potassium contents. Since amphibole is the
dominant liquidus phase controlling the residual melt
compositions in equilibrium crystallization experiments,
crystallization of an amphibole-dominated mineral
assemblage, accompanied by minor plagioclase crystal-
lization, could account for the trend observed for the
plateau series rocks. Moreover, the presented experi-
mental data suggest that fractionation at relatively high-
pressures and in a “closed system” (equilibrium or
quasi-equilibrium fractionation) could account for the
observed compositional trends.
Melt compositions obtained in the fractional crystal-
lization experiments match more closely the observed
natural rock compositions. The trends for FeO and Na2O
towards higher concentrations imply that the peralkaline
intrarift phase could possibly be generated by (poly-
baric) fractional crystallization from an identical
parental magma that produced the plateau series in an
earlier stage of rift evolution.
7. Conclusions
The natural rock data show clear distinctions
between plateau and intrarift silicic magmas. Since
geochemistry does not require differences of the
parental liquids between the Oligo-Miocene and the
Quaternary magmas, variation in the physical conditions
during differentiation have to account for the different
compositions of magmas erupted in these different
periods. After formation of the basaltic plateau by
fissural eruptions, residual magmas fractionated at lower
crustal levels (0.7–1 GPa), where dominantly amphi-
bole, and only subordinate plagioclase crystallization
drove the residual melt composition toward FeO and
Na2O-poor but Al2O3-rich subaluminous compositions.
During the last magmatic phase extensive crustal
thinning and intense fracturing of the crust allowed
rapid ascent of parental magmas from the lower crust
into shallow crustal magma reservoirs thereby enhanc-
ing differentiation/fractionation under low pressure
conditions. Experimental data presented in this study
evidence that the plagioclase stability in hydrous
parental magmas increases with decreasing pressure,
and can account for the Al2O3, FeO and alkalies trends
displayed by the Quaternary peralkaline trachytes and
rhyolites (Fig. 6).
The presence of water in magmas erupted in the
Ethiopian Rift system, as clearly suggested by the
presence of amphibole and the explosive nature of
eruptions, and the absence of any evidence supporting
active subduction indicates that either the mantle source
of the parental transitional basalts contained hydrous
phases (phlogopite and/or amphibole) or that H2O was
stored in nominally anhydrous minerals (NAMS,
Thompson, 1992).
Upwelling of a mantle plume produced a strong
thermal anomaly that either decomposed hydrous phases
or led to the extraction of H2O from NAMS (Aubaud et
al., 2004). The large dimension of the inferred plume
(Hofmann et al., 1997), that impinges at the base of the
lithosphere, combined with the strong concentration of
the magmatic activity into a relatively small area,
provides a mechanism that allows extraction of small
amounts of H2O from a large volume and its concentra-
tion into the primary liquids. Such a process results in
appreciable amounts of H2O (several wt.% of H2O) that
are required to stabilize amphibole phenocrysts (mainly
present in plateau phase rocks) during differentiation of
primary basaltic liquids and that are responsible for the
highly explosive character of the Plio-Quaternary
eruptions. An additional, important effect of water is
the increase of the anorthite and hence Al-content of
plagioclase for a given bulk composition (Yoder, 1969;
Sisson and Grove, 1993; Berndt et al., 2005). However,
to obtain very anorthitic plagioclase that could produce
the observed strong depletion of alumina with increasing
differentiation of the peralkaline, intrarift products, not
only hydrous conditions, but early plagioclase saturation
is a fundamental requirement that can only be achieved
through low pressure crystallization of rather primitive
parental magmas. Furthermore, H2O has an important
effect on the rheology and hence mobility of magmas. In
the reported experiments a decrease of pressure, at
constant bulk water content, results in an increase of the
crystallinity of the magmas due to increasing feldspar
 L. Caricchi et al. / Lithos 91 (2006) 46–58
stability. Therefore, migration of magmas into shallow
levels is rheologically only possible if parental magmas
contain relatively high amount of water and preferably
intrude into shallow levels prior to saturation with
plagioclase.
In conclusion, the MER primary mantle magmas are
hydrous and produce a variety of differentiated silicic
magmas through polybaric differentiation at crustal
levels. The tectonic evolution, or more precisely, the
maturation of the rift system is accompanied by
decreasing depths of the magma reservoirs where the
silica-rich differentiates are produced. This change in
principal differentiation pressure is reflected by the
transition from dominantly subaluminous to dominantly
peralkaline products with advancing rift evolution.
Acknowledgements
We gratefully acknowledge the financial support of
the first author by the Institute for Mineralogy and
Petrology at ETH Zürich. We thank Eric Reusser for his
assistance with the microprobe analysis. The original
version of this manuscript benefited considerably by the
detailed and thoughtful editorial comments by Gregor
Markl and reviews provided by Bruno Scaillet and an
anonymous reviewer.
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