Contrib Mineral Petrol (1998) 131: 323-346
Glenn A. Gaetani . Timothy L. Grove
The influence of water on melting of mantle peridotite
Received: 7 April 1997 / Accepted: 9 January 1998
Abstract This experimental study examines the effects of
variable concentrations of dissolved H20 on the com-
positions of silicate melts and their coexisting mineral
assemblage of olivine + orthopyroxene ± clinopyrox-
ene ± spinel ± garnet. Experiments were performed at
pressures of 1.2 to 2.0 GPa and temperatures of 1100 to
1345 °C, with up to ~12 wt% H20 dissolved in the
liquid. The effects of increasing the concentration of
dissolved H20 on the major element compositions of
melts in equilibrium with a spinel lherzolite mineral as-
semblage are to decrease the concentrations of Si02,
FeO, MgO, and CaO. The concentration of Ah03 is
unaffected. The lower Si02 contents of the hydrous
melts result from an increase in the activity coefficient
for Si02 with increasing dissolved H20. The lower
concentrations of FeO and MgO result from the lower
temperatures at which H20-bearing melts coexist with
mantle minerals as compared to anhydrous melts. These
compositional changes produce an elevated Si02/
(MgO + FeO) ratio in hydrous peridotite partial melts,
making them relatively Si02 rich when compared to
anhydrous melts on a volatile-free basis. Hydrous
peridotite melting reactions are affected primarily by the
lowered mantle solidus. Temperature-induced composi-
tional variations in coexisting pyroxenes lower the pro-
portion of clinopyroxene entering the melt relative to
orthopyroxene. Isobaric batch melting calculations in-
dicate that fluid-undersaturated peridotite melting is
characterized by significantly lower melt productivity
than anhydrous peridotite melting, and that the
G.A. Gaetani (1:8])1 . T.L. Grove
Department of Earth, Atmospheric and Planetary Sciences,
Massachusetts Institute of Technology,
Cambridge, MA 02139, USA
Present address:
'Division of Geological and Planetary Sciences,
California Institute of Technology,
Pasadena, CA 91125, USA
E-mail: gaetani@gps.caltech.edu
Editorial responsibility: J. Hoefs
© Springer-Verlag 1998
peridotite melting process in subduction zones is
strongly influenced by the composition of the H20-rich
component introduced into the mantle wedge from the
subducted slab.
Introduction
Water-bearing partial melts of mantle peridotite have
been the subject of experimental investigations and sci-
entific debate for the past 30 years. Our understanding
of the mantle melting process has increased significantly
over that time through the development of various direct
and indirect experimental approaches for determining
the compositions of anhydrous peridotite partial melts
(Ito and Kennedy 1967; Kushiro 1968; Presnall et al.
1979; Stolper 1980; Jaques and Green 1980; Falloon
and Green 1987; Kinzler and Grove 1992a,b; Hirose
and Kushiro 1993; Baker and Stolper 1994; Walter and
Presnall 1994; Baker et al. 1995; Kinzler 1997). Experi-
mental data bearing on hydrous peridotite partial melts
remain sparse. Water plays a central role in peridotite
melting at subduction zones, and accurate experimental
determinations of the effects of H20 on the composi-
tions and liquidus temperatures of peridotite partial
melts are necessary to advance our understanding of the
physical processes involved in melt generation at con-
vergent plate margins.
Much of our understanding of hydrous peridotite
melting comes from the pioneering experimental
studies of Kushiro and co-workers on simplified ana-
log systems such as Mg2Si04-SiOrH20 (Kushiro et al.
1968; Kushiro 1969, 1972). The results from these
studies suggested that hydrous peridotite partial
melting generates SiOrrich melts, and appeared to
support the hypothesis that subduction-related ande-
sites represent primary partial melts of hydrous mantle
peridotite (Poldervaart 1955; O'Hara 1965). Subse-
quent experimental work carried out on both analog
324

and natural compositions was focused on the origin of

andesite (Kushiro et al. 1972; Nichols and Ringwood
1972, 1973; Nichols 1974; Green 1973, 1976; Nehru
and Wyllie 1975; Mysen and Boettcher 1975a,b). Some
of the H20-bearing glasses produced in these studies
were characterized by high Si02 and low FeO and
MgO contents, and were cited as further evidence in
favor of the primary andesite hypothesis. These ex-
perimental results were controversial, however, and it
was suggested that the glass compositions had been
modified by the growth of amphibole and pyroxene
during the quench (e.g., Green 1973, 1976). Recent
experimental studies have produced H20-bearing par-
tial melt compositions that are broadly similar to
those produced by anhydrous peridotite partial melt-
ing (Kushiro 1990; Hirose and Kawamoto 1995).
Here we present the results from experiments per-
formed using natural mineral and rock compositions
that provide data on the nature of H20-bearing sili-
cate melts saturated with an upper mantle peridotite
mineral assemblage of olivine (Oliv) + orthopyroxene
(Opx) ± clinopyroxene (Cpx) ± spinel (Sp) ± garnet
(Gt). Comparisons of hydrous and anhydrous melt
compositions in both simple and natural systems dem-
onstrate that the defining characteristic of hydrous par-
tial melts of mantle peridotite is not an elevated Si02
concentration but an elevated Si02/(MgO + FeO)
ratio. The variation in this ratio with increasing dis-
solved H20 produces an apparent increase in the Si02
content of H20-bearing peridotite partial melts when
compared to anhydrous melts on a volatile-free basis.
Batch melting calculations show that although H20
increases the extent to which peridotite partially melts at
a given set of pressure-temperature conditions, melt
productivity at H20-undersaturated conditions is
significantly lower than during anhydrous peridotite
melting.
Experimental and analytical methods
Starting materials
Three natural basalts, a synthetic basalt analog, and 3 synthetic
peridotite compositions were used as starting materials for this
study (Table 1). The basalts were chosen to be close to saturation
with a lherzolite or harzburgite mineral assemblage at upper mantle
conditions, and to cover a range of incompatible element concen-
trations. Bulk compositions consisting of 60-70 wt% basalt and
30-40 wt% peridotite were melted to produce experimental charges
consisting of silicate melt saturated with a mantle peridotite min-
eral assemblage (Oliv + Opx ± Cpx ± Sp ± Gt) (Table 2). The
proportion of melt relative to crystals resulted in large areas (~100-
700 11m)of pristine glass in each experimental charge.
The starting material for each experiment was prepared by
weighing out the desired proportions of synthetic peridotite and
basalt, then grinding them in an agate mortar and pestle under
ethanol for 10 min. The bulk H20 content was controlled by
adding the basalt as either an anhydrous powder or as a H20-
bearing basaltic glass powder and, for some experiments, by adding
some proportion of a H20-bearing synthetic peridotite powder.
The consistent partitioning behavior of total Fe as FeO among
minerals and silicate melt in hydrous and anhydrous experiments
suggests that this method of adding H20 to the experiments results
in oxygen fugacity (f02) conditions comparable to those in anhy-
drous experiments performed in graphite crucibles (at or more re-
ducing than the C-CO-C02 buffer). Previous high-pressure
experimental studies have bracketed the f02 conditions for experi-
ments that initially contained liquid H20 to be between the Ni-NiO
and magnetite-hematite oxygen buffers, considerably more oxidiz-
ing than is the case for anhydrous experiments (Kushiro 1990;
Kawamoto and Hirose 1994).
Natural rock powders were prepared by crushing chips of clean,
fresh, aphyric lava in a WC shatterbox. Peridotite FP1 was syn-
thesized from mantle minerals separated from a Kilbourne Hole
spinel lherzolite xenolith (KH-5-4). A second peridotite composi-
tion (PUM), corresponding to the primitive upper mantle compo-
sition of Hart and Zindler (1986), and a synthetic basalt analog
corresponding to the composition of a small extent anhydrous
peridotite partial melt calculated using the method of Kinzler
(1997), were prepared from Johnson-Matthey high purity Si02,
Ti02, A1203, Cr203, Fe203, MnO, MgO, NiO, and previously
prepared mixes of CaSi03, Na2Si03, and K2Si409. These com-

Table 1 Compositions of starting materials. Units in parentheses synthetic mix. The composition and associated uncertainties for FP1
represent 1 standard deviation of least units cited on the basis of were calculated on the basis of electron microprobe analyses of mi-
replicate analyses; thus, 47.7(2) should be read as 47.7 ± 0.2. Re- neral separates from the Kilbourne Hole spinel lherzolite xenolith. (n
ported composition for PUM is the nominal composition of the number of electron microprobe analyses included in average)

Kilbourne Hole xenolith minerals

82-72f 85-44 93-26 DM151 PUM FP1 Cpx Opx Oliv Sp

n 25 25 25 25 27 25 21 25
Si02 47.7(2) 51.6(2) 50.9(2) 49.9(2) 45.97 44.9(2) 51.8(4) 54.8(4) 40.32(14) 0.06(2)
Ti02 0.62(3) 0.59(3) 1.28(4) 1.25(3) 0.18 0.18(1) 0.58(2) 0.12(2) 0.06(1) 0.11 (3)
Al203 19.05(9) 15.95(9) 17.7(2) 19.71(9) 4.06 4.27(5) 7.11(13) 4.7(2) 0.02(1) 57 .3(4)
Cr203 0.12(4) 0.16(4) 0.06(2) 0.14(4) 0.47 0.57(1) 0.72(2) 0.37(3) 0.08(2) 9.9(2)
FeO* 7.82(12) 8.08(12) 8.11(12) 6.80(11) 7.54 7.58(6) 2.70(6) 6.39(7) 9.80(11) 10.3(2)
MnO 0.15(5) 0.11(4) 0.15(3) 0.17(4) 0.13 0.11(1) 0.08(3) 0.1 0(3) 0.12(2) 0.10(3)
MgO 10.49(8) 11.30(9) 8.63(10) 9.33(7) 37.79 38.04(10) 15.5(2) 32.8(2) 49.8(2) 22.4(2)
CaO 11.75(9) 9.43(11) 8.89(6) 8.75(6) 3.21 4.28(2) 20.41(9) 0.71(2) 0.06(2) 0.02(1)
Na20 2.35(12) 2.59(12) 3.36(11) 3.4(2) 0.33 0.38(1) 1.76(5) 0.1 0(2)
K20 0.08(1 ) 0.31 (2) 0.74(2) 0.49(2) 0.03
P20S 0.08(2) 0.15(3) 0.31(3) 0.00
NiO 0.28 0.18(1 ) 0.32(2) 0.40(2)
Total 100.21 100.27 100.13 99.94 99.99 100.49 100.66 100.09 100.58 100.59
Mg# 70.5 71.4 65.5 71.0 89.9 89.9 91.1 90.1 90.1 79.5
Table 2 Experimental conditions and phase assemblages. Units in parentheses are 1a uncertainties

Experiment P T Duration Bas.perid'' Run products Phase proportions KD Fe

(GPa) (DC) (h) ratio (wt%) Cpx Opx Oliv Sp Gt ex-
change"

82- 72f Experiments

B333 1.2 1245 25 3.3(3)e 60:40 Gl, Cpx, Opx, 68.7(8): 1.5(6):9.4(7): 0.35 0.34 0.34 0.75 -0.88 0.02
Oliv, Sp 20.2(5):0.2(2)
B305 1.2 1230 24 4.5(5/ 64:36 Gl, Opx, Oliv, Sp 74.7(7):6.5(11): 18.5(6): 0.33 0.34 0.88 +2.5 0.06
0.4(2)
B304 1.2 1215 24 5.99(5)e 69:31 Gl, Cpx, Opx, 68.6(10):3.9(6): 10.8(6): 0.35 0.34 0.35 0.66 -0.39 0.02
Oliv, Sp 16.5(6):0.2(2)
B330 1.2 1200 29 5.06(4)e 70:30 Gl, Cpx, Opx, 71.2(9):6.8(6):4.4(9): 0.32 0.33 0.35 0.76 + 1.2 0.02
Oliv, Sp 16.9(6):0.7(2)
B329 1.2 1185 26 6.26(10)e 70:30 Gl, Cpx, Opx, 59.0(15): 14.4(9): 10.6(14): 0.29 0.32 0.34 0.58 +1.1 0.05
Oliv, Sp 13.8(9):2.2(3)
B326 1.2 1115 28 ~12 70:30 Qch, Cpx, Opx,
Oliv, Sp
B310 1.2 1100 24 ~12 70:30 Qch, Cpx, Opx,
Oliv, Sp
B303 1.2 1345 24 0.71 (17)[ 65:35 Gl, Cpx, Opx, 61.0(19): 12.4(17): 12.2(15): 0.34 0.31 0.32 0.49 + 1.2 0.07
Oliv, Sp 12.7(10): 1.7(3)
B292 1.2 1330 24 70:30 Gl, Cpx, Opx, 59.5(10): 18.9(8):8.3(9): 0.32 0.30 0.32 0.47 +0.65 0.02
Oliv, Sp 11.2(5):2.1 (2)
B287 1.2 1315 24 0.98(24/ 70:30 Gl, Cpx, Opx, 58.6(11): 16.9(1 0): 14.4(10): 0.33 0.30 0.32 0.49 +0.90 0.03
Oliv, Sp 7.7(6):2.4(2)
B359 1.6 1260 20 4.9(11 )e 70:30 Gl, Cpx, Opx, 67.1 (24):4.7(9):8.7(26): 0.35 0.33 0.34 0.56 0.59 -0.52 0.03
Oliv, Sp, Gt 1O.4(8):tr:9.1 (53)
B277g 1.6 1255 10 5.0(6/ 69:31 Gl, Cpx, Opx, 66.6(7):8.2(4): 11.4(5): 0.35 0.34 0.35 0.64 0.59 +0.39 0.008
Oliv, Sp, Gt 12.7(3): 1.1(l):tr
B348 1.6 1245 20 5.3(5)e 70:30 Gl, Cpx, Opx, 73.0(9):3.9( 6): 14.1(7): 0.34 0.33 0.34 0.59 -0.61 0.01
Oliv, Sp 9.0(4):tr
B366 1.6 1230 22 4.8(6)e 70:30 Gl, Cpx, Opx, 56.5(26):12.0(11):11.1(12): 0.33 0.34 0.36 0.66 +2.0 0.08
Oliv, Gt 8.3(9):12.1(18)
B394 1.6 1370 24 70:30 Gl, Cpx, Opx, 64.1 (15): 14.1(13): 15.2(12): 0.34 0.31 0.32 0.48 +0.89 0.05
Oliv, Sp 4.8(7): 1.8(2)
B302 1.6 1355 24 70:30 Gl, Cpx, Opx, 57.9(19):20.2(19): 15.1(15): 0.34 0.30 0.32 0.46 + 1.2 0.08
Oliv, Sp 4.2(9):2.6(3)
B365 2.0 1290 15 5.3(6)[ 70:30 Gl, Cpx, Opx, 60.6(29):9.0(15): 13.0(14): 0.34 0.35 0.36 0.63 +2.1 0.11
Oliv, Gt 3.3(8):14.1(18)
B399 2.0 1275 15 6.8( 4)e 70:30 Gl, Cpx, Opx, 63.6(10):7.9(5):8.5(5): 0.31 0.32 0.34 0.59 0.0 0.01
Oliv, Gt 6.1(3):13.9(6)
85-44 Experiments
B384 1.2 1200 30 5.19(7)e 70:30 Gl, Opx, Oliv 67.7(8):23.0(13):9.3(8) 0.31 0.33 +2.3 0.13
B388 1.2 1200 28 6.1(7)e 60:40 Gl, Opx, Oliv 61.6(8):21.1 (12): 17.3(8) 0.34 0.36 -0.85 0.12
B392 1.2 1170 30 7.87(12)e 60:40 Gl, Cpx, Opx, 46.0(4): 11.5(4):24.5(7): 0.33 0.33 0.36 -1.1 0.02
Oliv 18.0(4)
93-26 Experiments
B408 1.2 1200 24 5.6(8)e 70:30 Gl, Opx, Oliv 75.2(5): 14.0(9): 10.8(5) 0.31 0.33 -1.8 0.06
DM151 Experiments
B432 1.2 1185 26 6.2( 4)e 70:30 Gl, Cpx, Opx, 57.5(21 ):6.5(13):29.3(23): 0.28 0.28 0.31 0.58 +2.8 0.11
Oliv, Sp 4.1(15):2.3(4)
326

pounds were weighed out and ground automatically for 5 h, under

00
ethanol, using an agate mortar and pestle, after which FeD sponge
~ was added and the mix was ground for an additional h (Lindsley
o
et al. 1974). The resulting powder was pressed into 300 mg pellets,
using elvanol as a binder, and conditioned by sintering in a gas-
mixing furnace for 24 h at 1050 DC, with the f02 controlled at 1 log
unit below the fayalite-magnetite-quartz (FMQ) oxygen buffer
using a mixture of CO2 and H2 gases. A H20-bearing PUM
peridotite composition was synthesized from Johnson-Matthey
high purity Si02, Ti02, A1203, Cr203, MnO, NiO, and previously
prepared mixes of Fe2Si04, Mg(OHh, CaSi03, Na2Si03, and
K2Si409. These compounds were weighed out and ground auto-
matically for 6 h, under ethanol, using an agate mortar and pestle.
The Mg(OHh was synthesized following the methods described by
Johnson and Walker (1993) .
.2: Hydrous glasses were prepared by melting natural rock powder,
<5 or a synthetic basalt, in a titanium-zirconium-molybdenum (TZM)
rapid quench cold-seal pressure vessel at H20-saturated conditions.
Twenty-five III of distilled H20 were placed into a thick-walled Au
capsule, which was then packed with ~200-300 mg of rock powder
and welded shut. The charge was held at 200 MPa and 1050 DCfor
24 h, after which the experiment was terminated using the rapid
quenching technique of Sisson and Grove (1993a). The experi-
mental products were analyzed by electron microprobe, the relative
proportions of glass and crystals (Oliv + Sp ± Cpx ± Plag) were
determined by materials balance (Bryan et al. 1969), and the bulk
H20 content was calculated. The remaining material was ground
r ~ under ethanol using an agate mortar and pestle for 1 h for use as
~ ~ starting material in piston-cylinder experiments.
o 00
':: ;t:
~
M
~
~
~ ~ Capsule materials
M ~
N M
M M
~ ~ Maintaining a constant bulk composrtion is a prerequisite for
0\ ,-..,r- ,-..,
a:~[::::'~ producing an equilibrated experimental product. Capsules fabri-
~c:~r-: cated from Au are a good choice for hydrous melting experiments
.,......;("'1.,......;.,......;
because they minimize loss of Fe from the charge to the capsule and
they are less permeable to hydrogen than Pt, Ag, or AgPd alloys
(Chou 1985). Because the majority of our experiments were per-
formed at temperatures in excess of the melting point of Au, AuPd
alloys were used as capsule materials.
Iron loss from the silicate to unconditioned AU90PdlO capsules
was determined to be 30% relative after 24 h at 1.2 GPa and
1200 DC in experiments performed using hydrous glass starting
material, while in unconditioned AusoPd2o capsules Fe loss from
the silicate was determined to be 38% relative. Hirose and Kawa-
moto (1995) performed hydrous peridotite melting experiments in
AU7sPd2s capsules and reported no significant loss of Fe from the
silicate. A plausible explanation for the difference between our re-
sult and that of Hirose and Kawamoto (1995) is that the f02 in their
experimental charges was significantly higher than in our assem-
blies. The solubility of Fe in AuPd alloys is a strong function of the
ambient f02 conditions (Kawamoto and Hirose 1994), and there is
experimental evidence to indicate that the f02 conditions in ex-
periments that initially contain liquid H20, as opposed to hydrous
glass, tend to be oxidizing (Kushiro 1990; Kawamoto and Hirose
1994), The relatively low olivine/melt exchange K~e/Mg values
[K~e/Mg = (FeOcrystal x Mgomelt)/(Feomeit x MgocrYSt1H)]
(0.28 ± 0.01 versus 0.34 ± 0.01 for our hydrous experiments) and
molar olivine/silicate melt partition coefficients for total Fe as FeO
(~35% low relative to our experiments at a given temperature)
reported by Hirose and Kawamoto (1994) are consistent with rel-
atively high concentrations of Fe203 in their silicate melts. From
the above comparisons we conclude that unconditioned AuPd al-
loys do not behave as inert containers at the redox conditions of
typical anhydrous piston-cylinder experiments performed in
graphite crucibles.
Maintaining a constant bulk composition over the course of an
experiment required that each inner capsule be conditioned to
minimize Fe exchange with the silicate. For experiments in which
the AusoPd2o alloy was used the capsule was presaturated with a
basaltic liquid (82-72f) at 0.1 MPa and 1250 DC in a vertical gas-
mixing furnace for 48 hat anf02 1 log unit below the FMQ buffer.

Following the presaturation step, the silicate glass was removed
from the AuPd capsule using a warm HF bath. The ternary alloy in
the capsule from experiment B304, which experienced negligible Fe
exchange with the silicate after 24 h at 1.2 GPa and 1215 DCcon-
sists of 78.2 ± 0.6 wt% Au, 19.9 ± 0.2 wt% Pd, and
1.35 ± 0.05 wt% Fe. An andesitic liquid containing 7.23 wt%
FeO was used for presaturating the AU90PdlOalloy. These condi-
tioning runs were performed for 72 h at 1155 DC, with f02 con-
trolled at 2 log units below the FMQ buffer. The ternary alloy in
the capsule from experiment B359, which experienced negligible Fe
exchange with the silicate after 20 h at 1.6 GPa and 1260 DCcon-
sists of 88.5 ± 0.6 wt% Au, 10.0 ± 0.1 wt% Pd, and
0.68 ± 0.01 wt% Fe.
Experimental methods
Anhydrous and H20-undersaturated experiments were performed
using a 1.27 em solid-medium piston cylinder device (Boyd and
England 1960). Experiments were first pressurized to 1.0 GPa at
room temperature, then the temperature was raised to 865 DC at
100 DC/min. The pressure was then increased to the desired value,
and the experiment was held at these conditions for 6 min. Finally,
the temperature was increased at a rate of 50 DC/min to the desired
experimental conditions. The pressure medium consisted of sin-
tered BaC03, which was found to have a friction correction of
300 MPa through calibration against the pressure-dependent
melting point of Au (Akella and Kennedy 1971), and the Ca-
Tschermakite breakdown reaction (Hays 1966). This correction has
been applied to the pressures reported in Table 2. Pressures are
thought to be accurate to within ± 50 MPa. The temperature was
monitored and controlled using W97RerW7sRe2s thermocouples
with no correction for the effect of pressure on thermocouple EMF.
Temperatures reported in Table 2 are corrected for a 20 DC tem-
perature difference between the position of the thermocouple bead
and the hotspot, determined using offset thermocouples. Temper-
atures are thought to be accurate to ± 10 DC.
The assemblies for hydrous melting experiments were prepared
by packing ~ 15 mg of powder into a capsule made from either Au
(Experiments B310 and B326) or conditioned AU90Pd10 or
AUsoPd2oalloy, and welding it shut. The sealed inner capsule was
then placed into a graphite sleeve which was, in turn, placed into an
outer capsule made from either AUsoPt2oalloy or Pt, depending on
the temperature of the experiment. Graphite powder was packed
into the outer capsule, and it was welded shut. The sealed outer
capsule was placed into a high-density Al203 sleeve and centered in
the hotspot of a straight-walled graphite furnace using MgO
spacers.
The assemblies for anhydrous experiments were prepared by
packing ~6 mg of powder into a graphite crucible and placing a
graphite lid on top. The crucible was then placed into a Pt capsule,
and held at 120 DCin a drying oven for 14 to 65 h. Upon removal
from the oven, dried graphite powder was packed on top of the
crucible lid and the Pt capsule was welded shut. The sealed outer
capsule was then placed into an assembly identical to that used for
the hydrous melting experiments.
Analytical methods
All experimental run products were analyzed using either a 4- or 5-
spectrometer JEOL 733 electron microprobe at the Massachusetts
Institute of Technology. A 10 nA beam current and 15 kV accel-
erating potential were used for all analyses. Beam diameters were
20 11mfor hydrous glasses, 10-20 11mfor anhydrous glasses, and
2 11mfor crystalline phases. The hydrous glasses were analyzed for
° using a W /Si multilayer crystal (Nash 1992), with corundum as
an oxygen standard. Forty second peak counting times resulted in a
1o uncertainty due to counting statistics of ± 0.50% relative for 0.
Four hydrous basaltic glass secondary standards with H20 con-
tents of 2.11 to 6.17 wt% (Muenow et al. 1990; Sisson and Grove
1993b) were carbon-coated along with the unknowns, and analyzed
327
at the beginning of each microprobe session to determine the ac-
curacy and reproducibility of the ° analyses. On-line data reduc-
tion was accomplished using the phi-rho-z correction procedure.
Migration of Na from the excitation volume during analysis of the
hydrous glasses was minimized through use of a broad beam and
by measuring Na for 5 s prior to measuring the other elements
(Sisson and Grove 1993a). The maximum peak counting time for
the other elements was 40 s.
Replicate analyses of basaltic glass from an anhydrous, 0.1
MPa melting experiment (Experiment 839b-23 of Gaetani et al.
1994) were used to estimate analytical precision. Standard devia-
tions calculated on the basis of the distribution of 390 replicate
analyses performed over 37 months expressed as percent relative
are 0.52% for Si02, 0.90% for A1203, 0.98% for CaO, 1.3% for
MgO, 2.1% for FeO, 5.0% for Ti02, 6.5% for Na20, 6.7% for
K20, 31% for MnO, 38% for Cr203, and 65% for P20S. The mean
sum for the 390 analyses is 99.98 wt% (Table 3). Replicate analyses
of natural basalt glass 70-002 were used to determine whether use
of updated standards and the phi-rho-z correction procedure re-
sults in systematic deviations from previous analyses performed at
MIT using the correction procedure of Bence and Albee (1968),
with the modifications of Albee and Ray (1970). A comparison of
the mean of 30 replicate analyses with the analysis of the same glass
reported by Kinzler and Grove (1992a) is given in Table 3.
Glasses from five of the experiments were analyzed for both
H20 and CO2 by Fourier transform infrared (FTIR) spectroscopy,
following the general methods of Dixon et al. (1991) and modified
by the use of a NicPlan microscope (Table 4). For the high-Fl-O
glasses, each experiment was analyzed four times with the redun-
dant aperturing system set to 115 11mx 115 11m,while the nomi-
nally anhydrous experiments were analyzed twice each with a
20 11mx 30 11m aperture, using 1000 to 16000 scans. Sample
thicknesses ranged from 15 to 30 11m.
The H20 contents of the remaining experimentally produced
glasses were determined using a modified Cameca 3f ion probe at
Lawrence Livermore National Laboratory, using a 2 nA primary
beam (15-20 11m diameter) of 0- ions accelerated at 12.5 kV.
Sputtered ions were accelerated at a nominal 4.5 kV through a
double-focusing mass spectrometer, and H+, 160+, and 30Si+ ion
beams were measured with an electron multiplier. Samples were
measured at a mass-resolving power of ~500, and in order to
suppress isobaric molecular species and minimize matrix effects, an
energy offset of -80 ± 30 eV was used. Measured H+ /30Si+ ratios
were converted to wt% H20 by a calibration using 2 of the ex-
perimentally produced glasses that had been analyzed by FTIR
(B277 and B365), as well as natural and synthetic glasses provided
by S. Newman (Caltech) and J. Dixon (University of Miami).
A liquid nitrogen-filled cold trap was used to reduce the H20
background and the sample chamber vacuum. Background
H+ /30Si+ ratios measured on crystalline Oliv were in the range
~0.02-0.04, equivalent to ~0.1-0.2 wt% H20, and H+ /30Si+ ra-
tios measured on glasses were corrected for this background con-
tribution. Reported H20 contents represent averages of 3-5
individual measurements and reported uncertainties are the stan-
dard deviation of these measurements. For samples that were not
obviously heterogeneous this error is typically ± 10% relative (2Cl).
The reproducibility of an individual measurement, based on re-
peated standard measurements, is ± 15% relative (2Cl).
Experimental results
Hydrous experiments
Eighteen hydrous experiments produced silicate melts
saturated with a mantle peridotite mineral assemblage of
Oliv + Opx ± Cpx ± Sp ± Gt. Experiments per-
formed using the more aluminous basalt compositions,
82-72f and DM151, produced silicate melts saturated
 w
IV
00

Table 3 Electron microprobe analyses of run products from anhydrous experiments and anhydrous glass secondary standards. Units in parentheses as in Table 1. Analyses indicate
number of individual electron microprobe analyses included in average. (FeO* total Fe as FeO)

Experiment Phase Analyses Si02 Ti02 Al203 Cr203 FeO* MnO MgO CaO Na20 K20 P20S Total

Anhydrous experiments
B303 Gl 10 47.5(3) 0.66(3) 17.82(13) 0.17(4) 8.1 (2) 0.10(5) 11.80(10) 10.98(7) 2.17(13) 0.08(2) 0.12(3) 99.50
Cpx 15 51.5(8) 0.18(4) 8.0(11 ) 0.49(8) 4.9(2) 0.1 0(4) 20.9(11 ) 13.8(10) 0.49(3) 100.36
Opx 10 53.6(7) 0.12(2) 6.6(11 ) 0.35(7) 6.4(2) 0.1 0(3) 30.3(5) 2.3(2) 0.12(2) 99.89
Oliv 7 40.0(3) 0.05(3) 0.12(1) 0.06(4) 10.71(10) 0.1 0(3) 48.3(4) 0.31 (2) 99.65
Sp 5 0.53(10) 0.07(7) 62.1 (7) 4.5(3) 8.13(11) 0.11 (2) 24.0(3) 0.03(3) 99.47
B292 Gl 10 48.04(13) 0.68(2) 18.3(2) 0.13(3) 8.3(2) 0.16(3) 11.16(7) 10.57(7) 2.5(2) 0.12(1) 0.11 (3) 100.07
Cpx 15 51.7(7) 0.26(5) 8.9(9) 0.35(7) 4.8(3) 0.1 0(3) 20.1 (9) 14.3(10) 0.52(4) 101.03
Opx 10 53.2(6) 0.11 (3) 7.8(8) 0.28(3) 6.56(10) 0.15(3) 29.7(4) 2.11(14) 0.11(2) 100.02
Oliv 7 40.2(3) 0.05(2) 0.12(1) 0.14(3) 11.42(8) 0.1 0(2) 47.6(2) 0.27(1) 99.90
Sp 5 0.42(7) 0.14(1) 63.6(3) 3.2(3) 8.3(2) 0.08(2) 23.9(3) 0.07(2) 99.71
B287 Gl 10 46.9(2) 0.66(3) 17.90(10) 0.07(2) 8.41(11) 0.12(4) 11.41(11) 10.71(6) 2.50(11) 0.12(1) 0.13(2) 98.93
Cpx 15 51.7(6) 0.25(5) 8.4(9) 0.44(5) 4.8(2) 0.14(2) 19.9(8) 15.0(7) 0.56(3) 101.19
Opx 10 53.8(7) 0.12(3) 7.3(12) 0.35(6) 6.75(7) 0.13(2) 30.4(4) 2.08(7) 0.10(2) 101.03
Oliv 7 40.3(3) 0.02(2) 0.13(4) 0.09(3) 11.25(12) 0.12(2) 48.3(3) 0.27(2) 100.48
Sp 3 0.58(2) 0.08(3) 62.7(2) 4.64(9) 8.6(2) 0.09(0) 23.97(5) 0.08(2) 100.74
B394 Gl 10 46.3(2) 0.60(3) 17.08(14) 0.18(3) 8.62(8) 0.16(4) 12.99(12) 10.66(8) 2.22(5) 0.12(1 ) 0.14(2) 99.07
Cpx 15 51.5(5) 0.20(4) 8.7(6) 0.31 (3) 4.6(2) 0.11 (3) 20.6(4) 13.9(4) 0.63(3) 100.55
Opx 10 54.1(4) 0.12(3) 7.4(6) 0.35(2) 6.30(8) 0.11 (3) 30.6(4) 2.13(3) 0.12(1) 101.23
Oliv 6 40.2(3) 0.11(1) 0.03(8) 0.14(2) 10.41(7) 0.1 0(3) 49.5(2) 0.29(2) 100.78
Sp 2 0.38(3) 0.14(1) 64.2(5) 2.93(11 ) 7.92(11) 0.1 0(3) 25.0(2) 0.07(0) 100.74
B302 Gl 10 46.4(3) 0.68(4) 17.2(2) 0.13(3) 8.9(2) 0.11(4) 12.5(2) 10.75(13) 2.29(12) 0.07(2) 0.15(5) 99.18
Cpx 15 51.9(7) 0.20(7) 8.8(8) 0.29(4) 5.1(3) 0.11(4) 20.9(12) 12.8(12) 0.62(6) 100.72
Opx 10 53.0(5) 0.10(3) 7.3(9) 0.25(3) 6.50(5) 0.1 0(3) 30.1 (3) 2.16(10) 0.13(3) 99.64
Oliv 7 40.2(4) 0.08(3) 0.12(1) 0.10(3) 10.9(2) 0.07(5) 48.2(4) 0.31 (2) 99.98
Sp 4 0.7(2) 0.13(5) 64.4(4) 3.02(12) 8.00(11) 0.1 0(3) 24.33(3) 0.13(1) 100.81
B414 Cpx 15 52.3(6) 0.48(7) 6.7(8) 0.7(2) 4.0(2) 0.06(5) 18.8(7) 17.4(9) 0.88(8) 101.32
Opx 10 54.7(4) 0.20(3) 5.8(6) 0.55(7) 6.39(9) 0.10(5) 31.3(4) 1.66(8) 0.16(4) 100.86
Oliv 7 40.7(3) 0.09(2) 0.3(2) 0.14(5) 9.90(10) 0.1 0(3) 49.0(5) 0.3(2) 100.53
Sp 2 0.9(2) 0.34(1 ) 52.5(13) 14.5(12) 9.7(4) 0.09(6) 22.5(2) 0.22(2) 100.75
B412 Cpx 15 52.1(6) 0.44(4) 6.8(4) 0.68(8) 4.0(2) 0.05(6) 18.8(7) 16.8(8) 0.87(5) 100.54
Opx 10 54.4(4) 0.20(4) 6.1 (5) 0.57(5) 6.28(6) 0.08(5) 32.0(2) 1.52(4) 0.16(5) 101.31
Oliv 7 40.7(3) 0.02(2) 0.2(2) 0.17(2) 9.97(13) 0.12(6) 49.1(2) 0.16(1) 100.44
Sp 2 0.6(3) 0.33(1 ) 53.7(3) 14.0(4) 9.97(12) 0.10(1) 22.73(12) 0.09(1 ) 101.52
Anhydrous glass secondary standards
839b-23a 390 52.7(3) 0.65(3) 15.19(14) 0.12(5) 8.8(2) 0.15(5) 9.16(12) 11.36(11 ) 1.46(10) 0.26(2) 0.13(8) 99.98
839b-23b 10 53.3(2) 0.60(3) 15.16(8) 0.05(3) 8.85(8) 0.22(2) 9.36(5) 11.3(1) 1.48(5) 0.30(2) 0.11 (3) 100.73
70-002a 30 49.6(3) 1.28(3) 16.3(2) 0.10(5) 8.9(2) 0.16(4) 8.60(8) 11.88(13) 2.63(11 ) 0.09(2) 0.22(3) 99.76
70-002c 368 49.6(1) 1.20(2) 15.8(2) 8.98(7) 0.17(3) 8.66(6) 11.9(1) 2.67(6) 0.10(1) 0.12(4) 99.20

"This study
b Analysis from Gaetani et al. (1994)
c Analysis from Kinzler and Grove (1992a)

Table 4 Water and carbon dioxide concentrations of experi-
mentally produced silicate melts as determined by FTIR. For
FTIR analyses, units in parentheses represent uncertainty esti-
mates calculated by propogating uncertainties associated with
measurement of sample thickness (± 10% for high-HjO samples;
Experiment H20 (wt%) CO2 (wt%)
B305 4.5(5) 1.27(14)
B277 5.0(6) 1.19(13)
B365 5.3(6) 1.25(14)
B287 0.98(24) 0.07(2)
B303 0.71(17)
with a spinel and/or garnet lherzolite mineral assem-
blage at pressures of 1.2 to 2.0 GPa and temperatures of
1100to 1275 °C. Experiments performed using the lower
alumina compositions, 85-44 and 93-26, produced hy-
drous melts saturated with Oliv + Opx ± Cpx at
1.2 GPa and 1170 to 1200 0c.
Experimental charges contained large amounts of
silicate melt (46-75 wt%; Table 2) that, with the ex-
ception of the experiments described below, quenched to
produce homogeneous glasses containing 3.3 ± 0.3 to
7.87 ± 0.12 wt% H20 and ~1.25 wt% CO2 (Tables 4
and 5). The molar Mg/(Mg + Fe) ratio (Mg#) of the
glasses (calculated assuming all Fe as FeO) are 0.69 to
0.76. Mineral compositions are similar to those found in
natural peridotite. The forsterite (Fo) contents of the
Oliv range from 0.87 to 0.91, while the Mg# of the Opx
are 0.88 to 0.92. The Cpx have Mg# of 0.88 to 0.92 and
CaO contents of l7.3±0.3 to 21.2±OA wt% (all un-
certainties are 10").Detailed descriptions of the sizes and
morphologies of the crystalline phases in both hydrous
and anhydrous experiments are given by Gaetani (1996).
The silicate melt did not quench to a glass in the
experiments designed to produce melts with high
(~12 wt%) dissolved H20 contents. The melts in these
experiments underwent extensive modification due to
the growth of amphibole during the quench, and we
consider the glass compositions to be unreliable. The
compositions of the crystalline phases from 2 of these
experiments (B3l0 and B326) are reported in Table 5.
Ion probe analyses of several of the experimentally
produced glasses (B359; B366; B388) indicate significant
heterogeneity with respect to H20 (Table 6). The origin
of this heterogeneity is unknown. A comparison of the
ion probe analyses with electron microprobe analyses of
the 0 contents of the glasses requires unreasonably large
concentrations of dissolved CO2 (4-5 wt%) in order to
explain the lower H20 concentrations. Given the good
agreement between the 0 concentrations associated with
H20 and CO2 in experiments B305, B277, and B365
determined by FTIR and by electron micropro be
(Table 4) we used the results of the electron microprobe
o analyses to determine preferred H20 contents for the
experiments listed in Table 6. The preferred values rep-
resent averages of the individual ion probe analyses
which indicate the highest H20 contents. The standard
329
± 20% for low-Hjf) samples), goodness of spectra (negligible for
high-HyO samples; ± 13% for low-H-O samples), and molar
absorbance coefficient (± 5%). For electron microprobe ana-
lyses, units in parentheses are as in Table 1
°(wt%in Hby0FTIR)
2 + CO2 °(wt%in Hby0EMP)
2 + CO2
4.9(5) 4.9(2)
5.3(6) 5.7(4)
5.6(6) 5.1 (2)
deviations for H20 reported for these experiments were
calculated using all of the ion probe measurements in
order more accurately to reflect the variability found
among the individual analyses.
Anhydrous experiments
Anhydrous experiments were performed to provide a
baseline for interpreting the results of the hydrous ex-
periments. Five anhydrous experiments produced sili-
cate melts saturated with a mantle peridotite mineral
assemblage of Oliv + Opx + Cpx + Sp at pressures of
1.2 to 1.6 GPa and temperatures of 1315 to l370°C.
These experiments produced large amounts of silicate
melt (58-64 wt%; Table 2) that quenched to produce
homogeneous glasses with Mg# (calculated assuming all
Fe as FeO) of 0.71 to 0.73 (Table 3). The Fo content of
the Oliv range from 0.88 to 0.89, while the Mg# of the
Opx are 0.89 to 0.90. The Cpx have Mg# of 0.88 to 0.89,
and CaO contents of 12.8 ± 1.2 to 15.0 ± 0.7 wt%.
Two experiments performed on the PUM composition
at sub-solidus conditions produced Oliv + Opx +
Cpx + Sp mineral assemblages.
Approach to equilibrium
Several lines of evidence can be used to evaluate the
approach to equilibrium represented by our experi-
ments. First, a reversal of mineral compositions was
performed. Experiment B359 was carried out at 1.6 GPa
and 1260 °C using hydrous 82-72f glass and PUM
peridotite, which was synthesized from oxides, while
Experiment B277 was carried out at 1.6 GPa and
1255 °C using hydrous 82-72f glass and FPl peridotite,
which was synthesized from mantle minerals. The use of
different synthetic peridotites means that the minerals in
Experiment B359 crystallized from the hydrous glass
and synthetic oxide mix starting materials, while those in
Experiment B277 (with the exception of Gt) reequili-
brated through exchange among the melt and minerals,
as well as through the growth of new crystalline mate-
rial. There is good agreement between the compositions
of the crystalline phases in the two experiments
Table 5 Electron microprobe analyses of run products from H20-undersaturated melting experiments. Units in parentheses as in Table 1. Analyses indicate number of individual w
w
0
electron microprobe analyses included in average. (FeO* total Fe as FeO)

Experi- Phase Analyses Si02 Ti02 Ah03 Cr203 FeO* MnO MgO CaO Na20 K20 P20S H2O Total
ment

B333 Gl 10 45.8(3) 0.61(2) 17.06(10) 0.09(3) 6.87(11 ) 0.14(2) 11.44(7) 10.91(11) 2.03(13) 0.13(1) 0.09(4) 3.3(3) 98.47
Cpx 9 52.4(6) 0.14(5) 6.0(11 ) 0.9(2) 4.1 (2) 0.08(5) 19.4(8) 17.6(5) 0.49(5) 101.11
Opx 10 55.0(6) 0.09(3) 6.0(9) 0.8(1 ) 6.4(1 ) 0.13(4) 31.2(4) 1.7(1) 0.05(3) 101.37
Oliv 7 40.4(2) 0.01 (1) 0.07(1 ) 0.04(2) 10.03(8) 0.13(1) 49.9(2) 0.18(2) 100.76
Sp 2 0.17(2) 0.15(2) 49.4(17) 18.6(23) 10.0(2) 0.12(5) 22.20(8) 0.05(5) 100.69
B305 Gl 10 45.05(11) 0.54(3) 15.79(9) 0.17(3) 7.09(12) 0.12(4) 12.33(9) 10.33(11 ) 1.94(11 ) 0.05(2) 0.16(3) 4.5(5) 98.07
Opx 10 53.6(8) 0.08(4) 5.2(10) 1.0(2) 6.0(1 ) 0.09(4) 31.4(3) 1.6(1) 0.08(2) 99.05
Oliv 7 40.3(3) 0.1 0(2) 0.05(3) 0.08(3) 9.6(1) 0.14(3) 48. 7(4) 0.17(3) 99.14
Sp 2 0.31(1) 0.10(1) 41.1(17) 27.3(21) 10.6(4) 0.12(3) 21.0(2) 0.03(2) 100.56
B304 Gl 10 44.63(13) 0.59(4) 17.45(8) 0.05(5) 6.85(10) 0.08(6) 10.72(9) 10.72(13) 2.21(10) 0.08(3) 0.16(2) 5.99(5) 99.53
Cpx 15 51.3(5) 0.19(5) 7.2(7) 0.50(6) 3.9(1) 0.09(3) 17.6(3) 19.1(3) 0.50(3) 100.38
Opx 10 52.9(4) 0.09(6) 6.9(4) 0.50(6) 6.72(6) 0.12(6) 30.6(3) 1.63(9) 0.07(2) 99.53
Oliv 7 40.2(4) 0.05(3) 0.07(2) 0.12(3) 10.7(2) 0.17(5) 48.0(2) 0.21(2) 99.52
Sp 5 0.15(1) 0.11 (3) 58.9(16) 7.9(15) 9.6(2) 0.09(2) 23.0(4) 0.08(8) 99.83
B330 Gl 10 45.1 (2) 0.60(2) 17.63(8) 0.11 (2) 6.92(12) 0.12(2) 10.26(9) 10.22(9) 2.15(13) 0.10(1) 0.10(3) 5.06(4) 98.37
Cpx 15 52.0(3) 0.18(2) 6.2(5) 0.8(1 ) 3.9(1) 0.09(4) 18.0(3) 18.9(3) 0.43(2) 100.50
Opx 10 55.0(4) 0.09(2) 5.4(5) 0.71 (9) 7.0(1 ) 0.11 (3) 31.1 (2) 1.50(9) 0.04(2) 100.95
Oliv 7 40.5(2) 0.02(1) 0.06(1 ) 0.12(2) 11.3(2) 0.13(3) 48.3(3) 0.17(1) 100.60
Sp 5 0.3(2) 0.16(1) 54.0(8) 14.0(9) 10.9(1 ) 0.09(3) 21.3(4) 0.15(8) 100.90
B329 Gl 10 44.78(13) 0.63(2) 17.99(11) 0.08(3) 7.21 (13) 0.14(2) 9.39(11) 9.80(8) 2.31(13) 0.12(1) 0.08(2) 6.26(10) 98.79
Cpx 15 51.4(3) 0.22(3) 7.1 (5) 0.31(6) 3.9(2) 0.09(4) 17.5(4) 19.3(4) 0.51(3) 100.33
Opx 10 54.1 (7) 0.1 0(2) 6.5(7) 0.42(4) 7.41(7) 0.18(2) 30.5(3) 1.35(6) 0.06(1 ) 100.62
Oliv 7 40.3(1 ) 0.00(1) 0.06(2) 0.12(2) 12.2(1) 0.15(3) 47.3(2) 0.17(2) 100.30
Sp 5 0.3(3) 0.12(2) 63.0(5) 4.2(8) 10.0(2) 0.09(1 ) 22.5(2) 0.3(2) 100.51
B326 Cpx 15 52.3(5) 0.18(4) 4.6(6) 0.9(1 ) 2.8(2) 0.05(4) 17.5(4) 21.2(4) 0.37(4) 99.90
Opx 4 55.0(5) 0.07(1) 4.6(16) 0.8(2) 5.37(8) 0.09(4) 33.1(4) 1.2(1) 0.1(1) 100.33
Oliv 7 40.9(4) 0.05(3) 0.03(2) 0.06(4) 9.0(2) 0.12(4) 49.5(4) 0.13(2) 99.79
B310 Cpx 15 51.9(6) 0.32(3) 7.1 (7) 0.4(1 ) 3.6(2) 0.09(4) 16.6(3) 20.6(4) 0.42(5) 101.03
Opx 10 54.0(4) 0.13(3) 7.3(4) 0.33(5) 7.2(1 ) 0.12(4) 31.0(3) 1.2(1) 0.02(2) 101.30
Oliv 7 40.6(3) 0.02(2) 0.11(4) 0.08(2) 11.3(2) 0.13(2) 48.5(5) 0.18(2) 100.92
Sp 1 0.21 0.11 60.6 7.5 10.6 0.07 21.6 0.18 100.87
B359 Gl 10 43.9(2) 0.66(3) 17.19(13) 0.08(4) 7.36(11 ) 0.08(5) 11.79(8) 10.40(8) 2.37(12) 0.12(1 ) 0.15(4) 4.9(11 ) 99.00
Cpx 15 51.0(5) 0.17(3) 8.0(5) 0.37(8) 3.9(2) 0.10(5) 17.8(4) 18.1(6) 0.66(6) 100.10
Opx 10 53.6(5) 0.1 0(4) 7.1 (6) 0.33(5) 6.39(6) 0.12(3) 31.0(3) 1.55(7) 0.08(3) 100.27
Oliv 7 40.0(2) 0.02(2) 0.07(2) 0.04(5) 10.4(2) 0.10(4) 49.1(4) 0.18(2) 99.91
Sp 5 0.24(6) 0.05(6) 63.1(9) 4.2(8) 8.5(2) 0.07(4) 24.4(2) 0.11(3) 100.67
Gt 7 42.3(5) 0.18(6) 23.6(6) 0.66(7) 7.24(8) 0.27(4) 19.6(5) 6.5(4) 0.01(2) 100.36
B277 Gl 10 43.7(3) 0.59(3) 16.8(2) 0.08(2) 7.35(14) 0.16(2) 11.92(8) 10.48(8) 2.17(11) 0.09(1 ) 0.08(2) 5.0(6) 98.42
Rims Cpx 15 51.7(3) 0.19(7) 7.4(5) 0.6(1 ) 3.8(2) 0.08(4) 17.7(5) 18.8(4) 0.6(1) 100.87
Opx 10 54.3(5) 0.08(2) 6.5(6) 0.50(7) 6.6(1 ) 0.10(4) 30.9(4) 1.5(2) 0.06(2) 100.54
Oliv 7 40.7(2) 0.02(2) 0.06(1 ) 0.04(3) 10.7(2) 0.09(3) 48.8(3) 0.17(1) 100.58
Sp 5 0.16(3) 0.06(4) 60.1(13) 7.4(11) 9.2(2) 0.05(4) 23.3(4) 0.11(4) 100.38
Gt 7 42.8(2) 0.17(2) 24.0(3) 0.82(8) 7.1 (1) 0.26(2) 19.4(4) 6.5(5) 0.02(2) 101.07
Cores Cpx 3 52.5(4) 0.52(5) 7.5(3) 0.81(5) 3.1 (2) 0.11 (2) 15.3(4) 19.7(4) 1.5(2) 101.04
Opx 2 56.1 (1) 0.13(2) 4.81(2) 0.35(1 ) 7.2(4) 0.12(4) 32.1 (3) 0.76(1 ) 0.08(2) 101.65
B348 Gl 10 43.5(2) 0.64(4) 16.84(9) 0.09(3) 7.30(7) 0.15(4) 11.78(8) 10.52(12) 2.26(9) 0.05(3) 0.06(4) 5.3(5) 98.49
Cpx 15 51.5(3) 0.15(4) 7.7(4) 0.48(9) 3.8(1) 0.07(5) 18.1(3) 18.3(5) 0.60(3) 100.70
Opx 10 53.7(5) 0.03(3) 7.3(5) 0.38(5) 6.46(6) 0.09(4) 31.3(2) 1.55(8) 0.08(2) 100.89
Table 5 (continued)

Experi- Phase Analyses Si02 Ti02 Al203 Cr203 FeO* MnO MgO CaO Na20 K20 P20S H2O Total
ment

Oliv 7 40.4(2) 0.03(2) 0.02(2) 0.11(5) 10.4(2) 0.12(4) 49.2(5) 0.13(4) 100.41
Sp 2 0.20(3) 0.08(3) 63.0(3) 4.9(4) 8.65(1) 0.10(0) 23.76(9) 0.11 (3) 100.80
B366 Gl 10 44.2(3) 0.66(3) 16.82(9) 0.12(2) 7.77(8) 0.13(3) 11.43(12) 9.86(13) 2.42(12) 0.11 (2) 0.16(2) 4.8(6) 98.48
Cpx 15 51.6(5) 0.19(6) 7.1(10) 0.32(7) 4.1(1) 0.06(5) 18.2(4) 18.4(4) 0.45(3) 100.42
Opx 10 54.5(8) 0.03(6) 6.1 (7) 0.3(1) 7.0(3) 0.10(5) 30.7(10) 1.8(10) 0.07(3) 100.60
Oliv 7 40.3(2) 0.06(4) 0.04(3) 0.04(2) 11.7(2) 0.13(2) 48.3(2) 0.17(4) 100.74
Gt 9 41.8(2) 0.18(5) 23.3(2) 0.7(1) 8.3(1) 0.32(4) 18.6(2) 6.8(2) 0.02(2) 100.02
B365 Gl 10 43.88(13) 0.64(2) 15.41(5) 0.15(3) 8.21(13) 0.12(5) 13.36(10) 10.25(10) 2.2(2) 0.10(2) 0.09(2) 5.3(6) 99.71
Cpx 15 52.7(4) 0.12(4) 6.2(2) 0.26(6) 4.1(1) 0.09(4) 19.4(2) 17.3(3) 0.48(2) 100.65
Opx 10 55.2(4) 0.11 (3) 5.6(4) 0.29(5) 6.7(1 ) 0.10(4) 31.3(2) 1.71(7) 0.06(3) 101.07
Oliv 7 40.5(3) 0.01(2) 0.05(2) 0.13(4) 10.75(6) 0.09(4) 48.6(3) 0.20(2) 100.33
Gt 10 42.1 (4) 0.11(4) 23.7(3) 0.6(1) 7.54(9) 0.27(2) 19.5(2) 5.9(3) 0.00(1 ) 99.72
B399 Gl 10 43.6(2) 0.65(2) 15.03(9) 0.07(3) 7.74(10) 0.11 (5) 12.70(6) 9.84(12) 2.41(10) 0.12(2) 0.21(2) 6.8(4) 99.28
Cpx 15 53.1(4) 0.17(2) 6.0(4) 0.18(5) 3.6(1 ) 0.10(3) 19.0(3) 18.0(4) O.76(4) 100.91
Opx 10 55.9(4) 0.09(2) 4.7(7) 0.21(5) 6.24(9) 0.07(3) 32.2(2) 1.65(7) 0.09(2) 101.15
Oliv 6 40.5(3) 0.11 (2) 0.10(3) 0.02(2) 10.2(1 ) 0.16(2) 49.6(2) 0.27(3) 100.96
Gt 10 42.2(2) 0.14(3) 23.9(2) 0.5(1) 7.1(2) 0.25(2) 19.9(2) 6.1 (1) 0.01 (1) 100.10
B384 Gl 10 45.90(10) 0.57(3) 15.75(11) 0.12(3) 7.39(14) 0.11 (3) 10.25(9) 9.47(13) 2.71(13) 0.35(2) 0.21(3) 5.19(7) 98.02
Opx 10 55.4(3) 0.10(4) 4.1 (2) 0.66(9) 7.2(1 ) 0.13(5) 32.0(2) 1.43(7) 0.06(2) 101.08
Oliv 7 40.4(2) 0.02(1) 0.08(4) 0.15(2) 11.6(1 ) 0.15(4) 48.6(2) 0.15(1) 101.15
B388 Gl 10 45.8(2) 0.57(3) 15.6(2) 0.15(3) 6.65(10) 0.1 0(2) 10.41(6) 9.55(7) 2.66(9) 0.35(2) 0.15(2) 6.1(7) 98.09
Opx 10 55.7(2) 0.1 0(3) 4.2(2) 0.71(7) 7.0(1 ) 0.16(2) 32.0(2) 1.31(7) 0.04(2) 101.22
Oliv 7 41.1(2) 0.01 (1) 0.08(2) 0.03(1) 11.1(1) 0.10(3) 48.7(2) 0.13(1) 101.25
B392 Gl 10 46.2(3) 0.68(3) 18.0(3) 0.06(3) 6.4(2) 0.08(3) 8.48(9) 8.82(4) 3.0(2) 0.44(2) 0.22(3) 7.87(12) 99.88
Cpx 15 51.9(4) 0.28(3) 6.7(7) 0.65(9) 4.2(1 ) 0.12(2) 17.2(3) 19.2(4) 0.62(6) 100.87
Opx 10 54.6(3) 0.1 0(2) 6.3(3) 0.59(9) 7.7(1 ) 0.14(3) 30.6(2) 1.37(7) 0.07(1) 101.32
Oliv 7 40.7(2) 0.11 (2) 0.09(2) 0.07(2) 12.7(2) 0.17(2) 47.3(2) 0.18(2) 101.32
B408 Gl 10 46.8(2) 1.20(3) 16.18(6) 0.12(3) 6.97(12) 0.10(4) 9.74(7) 8.90(9) 3.06(11) 0.70(3) 0.32(3) 5.6(8) 99.69
Opx 10 55.3(2) 0.19(2) 4.4(2) 0.75(4) 7.04(7) 0.13(3) 31.8(2) 1.53(4) 0.07(2) 101.21
Oliv 7 40.3(1 ) 0.05(2) 0.05(3) 0.1 0(3) 11.5(1 ) 0.13(3) 48.9(1 ) 0.17(1) 101.20
B432 Gl 10 45.8(2) 1.26(4) 18.13(10) 0.02(1 ) 6.97(11) 0.17(3) 8.76(8) 8.91(8) 3.59(9) 0.48(1) 6.2(4) 100.29
Cpx 15 51.6(4) 0.53(6) 7.7(5) 0.61(18) 3.8(2) 0.06(5) 17.2(4) 18.9(6) 0.80(4) 101.20
Opx 10 54.3(3) 0.20(3) 7.0(3) 0.48(11 ) 6.9(3) 0.16(5) 30.7(2) 1.43(11 ) 0.08(2) 101.25
Oliv 7 40.4(2) 0.1 0(3) 0.05(3) 0.07(3) 12.0(2) 0.15(6) 48.3(2) 0.15(1) 101.22
Sp 3 0.29(16) 0.17(1) 61.2(2) 6.2(2) 10.68(5) 0.10(4) 23.0(3) 0.09(3) 101.73
332
Table 6 Water contents of experimentally produced silicate melts
that appear to be heterogeneous with respect to H20 as determined
by ion microprobe
Experiment Range of H2O Preferred H2O
contents (wt%) content (wt%)
B359 1.45-4.25 4.19
B366 3.14-4.96 4.81
B388 3.66-6.07 6.07
(Table 5), indicating that diffusion rates are fast enough
under hydrous conditions to reequilibrate the rims of the
mineral grains in 10 h. The cores of the larger pyroxene
grains in Experiment B277 have compositions similar to
the starting material (Tables 1 and 5), indicating that
bulk equilibration of the charge was not achieved.
The maintenance of constant sample bulk composi-
tion is essential for equilibration, and has been demon-
strated by materials balance (Table 2). The achievement
of consistent mineral/melt exchange equilibrium indi-
cates a close approach to equilibrium. The average ex-
change K~e/Mgvalues for olivine (0.34 ± 0.01 versus
0.33 ± 0.03), clinopyroxene (0.33 ± 0.02 versus
0.36 ± 0.04), orthopyroxene (0.32 ± 0.02 versus
0.33 ± 0.04), spinel (0.60 ± 0.13 versus 0.54 ± 0.06),
and garnet (0.61 ± 0.03 versus 0.54 ± 0.06) are in
agreement with those from the longer duration (18-
112 h, with a mean duration of 66 h), anhydrous ex-
periments of Kinzler (1997).
Discussion
The compositions of hydrous melts of mantle peridotite
Evaluating the effects of dissolved H20 on the compo-
sitions of peridotite partial melts requires a comparison
of hydrous and anhydrous partial melts of the same
silicate bulk composition. Although recent experimental
work has provided compositional data for hydrous sili-
cate melts in equilibrium with mantle peridotite (Ku-
shiro, 1990; Hirose and Kawamoto 1995; Hirose 1997;
Kawamoto and Holloway 1997), comparisons of the
compositions of anhydrous and hydrous partial melts
have been carried out only on a volatile-free basis. This
type of comparison is useful for interpreting the com-
positions of subduction-related lavas, but it does not
allow an evaluation of thermodynamic controls on the
compositions of H20-bearing peridotite partial melts. In
the discussion that follows, a comparison of the com-
positions of hydrous and anhydrous silicate liquids in
equilibrium with a spinel lherzolite mineral assemblage
is carried out in 2 ways: (1) with H20 included as a
component to identify thermodynamic controls on the
compositions of hydrous peridotite partial melts; (2)
with melt compositions normalized on a volatile-free
basis (hereafter referred to as apparent compositions) to
identify the compositional characteristics of degassed
primitive arc and back-arc lavas, and to place con-
straints on the composition of material transferred from
the mantle to the crust by island arc magmatism.
The ternary system Mg2Si04-SiOrH20 provides a
useful starting point for discussing the effects of H20 on
the compositions of peridotite partial melts. Kushiro
et al. (1968) demonstrated that the incongruent melting
behavior of enstatite (En), which disappears at pressures
of ~0.5 GPa under anhydrous conditions (Boyd et al.
1964), persists to at least 3.0 GPa when H20 is present
in the system. Experimental work on the system CaO-
MgO-AhOrSiOrNa20-H20 further demonstrated that
H20-bearing silicate melts saturated with Fo and En are
quartz normative to pressures of at least 2.5 GPa (Ku-
shiro 1969, 1972).A reexamination of the experiments of
Kushiro et al. (1968) demonstrates that when H20 is
included as a melt component the liquids produced by
the incongruent melting of En have lower Si02 contents
than anhydrous En melts formed at the same pressure.
The elevated Si02 concentrations that are commonly
associated with hydrous En + Fo-saturated melts are
an artifact of comparing liquid compositions on a vol-
atile-free basis.
Under anhydrous conditions En melts congruently at
1.0 GPa to form a liquid containing 60 wt% Si02. The
bulk composition of an H20-undersaturated experiment
performed by Kushiro et al. (1968) at 1.0 GPa is rep-
resented by the open circle in Fig. 1 (91 wt%
En + 9 wt% H20). The composition of the hydrous
melt produced in this experiment could not precisely be
P= 1.0 GPa
Weight Units
T = 1375°C
Fig. 1 Ternary system Mg2Si04-H20-Si02 illustrating phase relations
relevant to determining the compositions of liquids produced by
melting MgSi03 + H20 at 1.0 GPa. Open circle represents the bulk
composition (91 wt% MgSi03 + 9 wt% H20) of a fluid-undersat-
urated melting experiment performed by Kushiro et al. (1968) at
1.0 GPa and 1375 "C. Possible compositions of the experimentally
produced silicate liquid coexisting with forsterite and enstatite at these
conditions, as determined from three-phase triangles, are represented
by the black triangle. The shaded region represents all possible liquid
compositions with Si02 contents equal to or greater than a liquid
produced by melting anhydrous MgSi03 at 1.0 GPa. The field of fluid
compositions (vertical lines) is approximate.
 333

determined, but the coexistence of En + Fo + liquid,
with no fluid phase, requires that it lie within the black
triangle shown in Fig. 1. The melt composition is con-
strained by the coexistence of Fo and En to lie on the
SiOrrich side of the MgSiOrH20 join, above an ex-
tension of the line connecting the F 0 apex of the ternary
to the bulk composition (dashed line labeled En out).
The lack of a fluid phase requires the H20 content of the
melt to be less than the saturation value of ~ 11 wt%.
This geometric analysis demonstrates that when H20 is
included as a melt component, the range of possible
hydrous liquid compositions have Si02 contents (~53-
57 wt% Si02) lower than 60 wt%. Although the absol-
ute concentration of Si02 is lower in the hydrous En
partial melts they are characterized by an elevated Si02/
MgO ratio, making them quartz normative. When pro-
jected from H20 onto the Fo-Si02 join and considered
on an anhydrous basis, this increased Si02/MgO ratio
produces a range of possible volatile-free liquid com-
positions that have Si02 contents (60-64 wt%) equal to
or greater than the anhydrous En melt.
Our experiments on natural starting compositions
demonstrate that these observations also hold for melt-
ing of mantle peridotite. Figure 2 contains plots of wt%
Si02 (Fig. 2a) and wt% Ah03 (Fig. 2b) versus molar
Mg/(Mg + Fe) ratio comparing the compositions of
our experimentally produced hydrous (3.3 ± 0.3 to
6.26 ± 0.10 wt% H20) and nominally anhydrous
(:'::1wt% H20) silicate melts in equilibrium with a spinel
lherzolite assemblage at 1.2 GPa. When H20 is included
Fig. 2a, b Plots of molar Mgj(Mg + Fe) ratio versus the weight
concentrations of: a Si02; b Al203, comparing the compositions of
experimentally produced anhydrous (filled symbols) and hydrous
(open symbols) silicate melts saturated with a spinel lherzolite mineral
assemblage at 1.2 GPa and 1185-1345 "C. Water has been included as
a component in all liquid compositions. Experiments performed using
mixtures of 82-72f basalt and PUM peridotite are represented by
circles. Experiment performed using a mixture of DM151 basalt
analog and PUM peridotite is represented by a triangle. (Vertical error
bars 1o values from Tables 3 and 5, horizontal error bars 1o values
calculated by propagating the standard deviation of the mean for FeO
and MgO from Tables 3 and 5)
as a component, the Si02 contents of the hydrous melts
are lower than those of the anhydrous melts by ~2 to
3 wt%, just as in the system Mg2Si04-SiOrH20. The
concentration of Ah03 is largely unaffected by the
presence of dissolved H20. The Si02 content of the melt
from the experiment performed using the DM15l syn-
thetic basalt (open triangle) is ~ 1 wt% higher than the
lower alkali H20-bearing melt with a comparable Mg#,
but the Si02 versus Mg# trend formed by the 82-72f
experiments is poorly defined. The A1203 content of the
higher alkali hydrous melt is comparable to the Ah03
contents of the lower alkali melts.
Thermodynamic controls on the Si02 contents of
H20-bearing peridotite partial melts can be determined
by calculating the activity of Si02 (a~:6) in each of the
experimentally produced silicate liquids. The coexistence
of Oliv, Opx and liquid fixes a~:6 for a given set of
pressure-temperature conditions, aJd the reaction:
Mg2SiO~liv + SiO~iq = Mg2Si20~PX
can be used to calculate a~i62
values on the basis of the
compositions of coexisting Oliv and Opx (Carmichael
et al. 1970; Morse 1979; Ghiorso et al. 1983; Grove and
Juster 1989). The Si02 activity coefficients (y~i6 )
can
then be determined by dividing a~:62
by the mol~ frac-
tion of Si02 in the melt. Calculations were carried out
using two different combinations of standard state
thermodynamic properties and mixing models for Oliv
and Opx (Table 7). Although the 2 sets of calculations
resulted in different a~:62
values, both indicated the same
Y~:6 dependencies. The compositions of anhydrous liq-
uid~ saturated with a minimum assemblage of Oliv +
Opx at 1.2 GPa have been included from the study of
Kinzler and Grove (l992a) to extend the database.
The results from the a~i62
calculations are presented
in Table 7 and in Fig. 3. There is a weak temperature
dependence for a~i62
so that, if y~i62
remained constant,
the concentration of Si02 in the hydrous liquids would
be slightly lower than in the anhydrous liquids due to
their lower liquidus temperatures. A plot of lnY~:62
versus inverse temperature (Fig. 3a) demonstrates that
y~i62 is not constant. Some of the y~i62
variability found

49 ,-...,---r---r,-....,-,---.---r----, 19 .----..---r----r-....,-,...---,--'.--,
P= 1.2 GPa P= 1.2GPa
~
~
-
Qi
:2 47
48 -+
Anhydrous

+
+ +-+-: +++ Anhydrous

.~
~+
~
.f:
46
+ + Hp+ 3.3 - 6.3 wt%
3.3 - 6.3 wt%
H20
+
-+-
®. . +
44 16
. . , .
0.68 0.70 0.72 0.74 0.76 0.68 0,70 0.72 0.74 0.76
Molar Mg/(Mg+Fe) of Silicate Melt Molar Mg/(Mg+Fe) of Silicate Melt
334

Table 7 Data used to calculate Si02 activity coefficients for experimentally produced silicate melts
XMe1t,a XMe1t,a Oliv,b Opx,c Melt,d Melt,e Oliv,f Opx,g Melt,h Melt,i
Experiment T(°C) H2O Si02
aFo aEn aSi02 YSi02 aFo aEn aSi02 YSi02

B333 1245 0.114 0.469 0.819 0.570 0.255 0.544 0.809 0.765 0.289 0.616
B305 1230 0.146 0.445 0.821 0.587 0.260 0.585 0.812 0.784 0.293 0.659
B304 1215 0.191 0.428 0.803 0.548 0.247 0.576 0.792 0.765 0.291 0.681
B330 1200 0.167 0.449 0.797 0.565 0.254 0.567 0.785 0.756 0.283 0.630
B329 1185 0.202 0.435 0.782 0.542 0.247 0.568 0.768 0.747 0.270 0.622
B384 1200 0.168 0.447 0.794 0.584 0.264 0.590 0.782 0.762 0.286 0.639
B388 1200 0.202 0.430 0.801 0.587 0.263 0.612 0.790 0.766 0.285 0.661
B392 1170 0.241 0.426 0.776 0.538 0.246 0.577 0.760 0.741 0.256 0.601
B408 1200 0.179 0.446 0.796 0.579 0.261 0.585 0.784 0.759 0.284 0.636
B432 1185 0.197 0.435 0.788 0.541 0.245 0.563 0.775 0.757 0.272 0.625
356 1250 0.158 0.462 0.804 0.619 0.282 0.611 0.793 0.752 0.290 0.629
357a 1200 0.205 0.439 0.774 0.594 0.275 0.627 0.759 0.791 0.306 0.696
357b 1200 0.298 0.393 0.816 0.642 0.282 0.718 0.807 0.788 0.287 0.729
358 1150 0.148 0.477 0.792 0.551 0.244 0.512 0.778 0.754 0.236 0.495
B303 1345 0.026 0.523 0.801 0.563 0.268 0.512 0.791 0.745 0.297 0.568
B292 1330 0.543 0.790 0.541 0.260 0.478 0.778 0.741 0.299 0.551
B287 1315 0.036 0.514 0.794 0.549 0.260 0.507 0.783 0.743 0.297 0.577
B29 1315 0.536 0.810 0.563 0.262 0.489 0.801 0.784 0.306 0.572
B32 1285 0.546 0.703 0.499 0.264 0.484 0.679 0.721 0.329 0.603
B30 1300 0.537 0.744 0.529 0.266 0.495 0.727 0.736 0.315 0.587
B52 1315 0.539 0.771 0.546 0.267 0.495 0.757 0.759 0.314 0.582
B54 1285 0.553 0.782 0.522 0.249 0.450 0.769 0.762 0.307 0.555
B55 1270 0.551 0.780 0.513 0.243 0.442 0.766 0.750 0.302 0.548
B59 1285 0.551 0.767 0.527 0.256 0.464 0.752 0.776 0.320 0.581

a Mole fraction of oxide component in silicate melt calculated using
the components of Bottinga and Weill (1972)
b Calculated relative to a standard state of pure forsterite at the P
and T of interest using standard state properties from Berman
(1988) and the mixing model of Hirschmann (1991)
C Calculated relative to unit activity of pure clinoenstatite in or-
thopyroxene at the P and T of interest using standard state prop-
erties from Berman (1988) and the mixing model of Sack and
Ghiorso (1994)
d Calculated relative to a standard state of pure Si02liquid at the P
and T of interest using a~~v and a~~x from columns 5 and 6, with
liquid standard state properties calculated using data from Berman
(1988), Richet et al. (1982), Lange and Carmichael (1990), and
Ghrioso and Sack (1995)
e Calculated using values from columns 4 and 7
f Calculated relative to a standard state of pure forsterite at the P
and T of interest using standard state properties from Davidson
and Lindsley (1989) and the mixing model of Davidson and Mu-
khopadhyay (1984)
g Calculated relative to pure enstatite at the P and T of interest
using standard state properties from Davidson and Lindsley (1989)
and the mixing model of Davidson and Lindsley (1985, 1989)
h Calculated relative to a standard state of pure Si02 melt at the P
and T of interest using a~~v and a~~x from columns 9 and 10, with
liquid standard state properties calculated using data from Helge-
son et al. (1978), Richet et al. (1982), Lange and Carmichael (1990),
and Ghrioso and Sack (1995)
I Calculated using values from columns 4 and 11

among the anhydrous experiments (filled circles) is at-
tributable to temperature dependence (solid line), cal-
culated by assuming that the partial molar excess free
energy of mixing is independent of temperature (Ryer-
son 1985; Hirschmann et al. in press). The Y~:6 values
2
calculated from the hydrous experiments (open circles)
are larger than would be predicted on the basis of the
L'
temperature dependence of the anhydrous Ys:6 values,
indicating that there is a significant dependence ~n liquid
composition (Fig. 3a).
When all of the Y~:6values in Fig. 3a are corrected to
an intermediate tempdrature (1250 "C), there is a posi-

-.35 -.25 , ,
o Hydrous Mells (This Study)
• Anhydrous Melts (This Study; c H~drous Mells "
-.35 ( ushiro, 1990)
-.45 Kinzler & Grove, 1992)
P=1.2GPa 0
-.45
-.55
o
o
8 o :'2 (\J
0 "
~ON
o 8 5-0 "
00
0
:.:JU5 ~ <ii-.55 o 0 qp
?- o
.E
.E -.65 0
Temperature
• Dependence -.65 "
......._of Iny.§~u~d
-.75
-.75
•• P= 1.2 GPa

® •• ® T = 1250°C
-0.85 -0.85 L.-----I._-'-_...L..._.L----'_-l.._-'
6.0 62 6A 6~ 6B 7.0 0.0 0.050.100.150.200.250.300.35
10,0001T (K) H20 in Silicate Melt (Mole Fraction)
 335

12 ,
Anhydrous ~
P= 1.2 GPa --9-
-=t= +
Anhydrous
i --+-

+ (j)
:2
11

+-
-+

2 10
C1l
g 3.3 - 6.3 wt%
Ui -+- H<!O
3.3 -6.3 wt%
+++ .s
0
Cl
9
--<>-
H<!O :2
@ P= 1.2 GPa
® , 8L---..L_-'----''---L_...J....---''---.L.---l
6
0.68 0.70 0.72 0.74 0.76 0.68 0.70 0.72 0.74 0.76
Molar Mg/(Mg+Fe) of Silicate Melt Molar Mg/(Mg+Fe) of Silicate Melt

Fig. 4a, b Plots of molar Mgj(Mg + Fe) ratio versus the weight
concentrations of: a FeO; b MgO, comparing the compositions of
nominally anhydrous (filled symbols) and H20-bearing (open symbols)
silicate melts saturated with a spinel lherzolite assemblage at 1.2 GPa
and 1185-1345 DC.Water has been included as a component in all
liquid compositions. Symbols are the same as in Fig. 2 (Vertical error
bars 1o values from Tables 3 and 5; horizontal error bars 1o values
calculated by propagating the standard deviation of the mean for FeO
and MgO from Tables 3 and 5)
tive correlation between lny~f6 and the mole fraction of
H20 dissolved in the liquid (Fig. 3b). This correlation is
also evident in the hydrous basalt-peridotite sandwich
experiments of Kushiro (1990) (open squares), and the
combined database suggests that y~t62
increases con-
tinuously up to ~30 mol% H20. The positive correla-
tion in Fig. 3b indicates a progressively smaller
deviation from ideal mixing for Si02 with increasing
H20, and is the opposite of what would be expected
from the formation of hydroxyl groups through the in-
teraction of H20 with bridging oxygens (e.g., Kushiro
1975; Stolper 1982). Although it is possible that this
••
Fig. 3 a Plot illustrating the relationship between In Y~:6
and inverse
temperature for experimentally produced anhydrous (jilled circles)
and hydrous (open circles) silicate melts saturated with a mantle
peridotite mineral assemblage (Oliv + Opx ± Cpx ± Sp) at
1.2 GPa and 1170-1345 DC. Data are from this study and from
Kinzler and Grove (l992a). The In y~i6 values and the temperature
dependence of In y~i6 from an anhydrous liquid (solid line) were
calculated as discussed in the text. b Plot illustrating the relationship
between the mole fraction of H20 dissolved in a silicate melt and
In y~i6for nominally anhydrous (filled symbols) and H20-bearing
(open Iymbols) silicate melts saturated with a mantle peridotite mineral
assemblage (Oliv + Opx ± Cpx ± Sp) at 1.2 GPa and 1250 DC.
Activity coefficients have been corrected to a single intermediate
temperature (1250 DC)as discussed in the text. Open squares represent
experimentally produced H20-bearing silicate liquids from Kushiro
(1990). Circles represent data from this study and from Kinzler and
Grove (1992a). The standard state free energy of pure SiCh liquid at
the pressure and temperature of interest was determined by first
calculating the Gibbs free energy of ~-cristobalite at its 0.1 MPa
melting point (1999 K) using thermochemical data from Berman
(1988). The Gibbs free energy of pure SiCh liquid at the pressure and
temperature of interest was then calculated using enthalpy of fusion
and heat capacity data from Richet et al. (1982) and molar volume
data from Richet et al. (1982), Lange and Carmichael (1990), and
Ghiorso and Sack (1995). The heat capacity was assumed to be
temperature dependent below the glass transition (1206.85 DC)
trend results directly from interactions between Si02 and
H20 in the melt, it may also be produced indirectly
through variations in melt composition or the speciation
of melt components related to increasing H20. For ex-
ample, there is a tendency for y~t62
to decrease with in-
creasing alkalis in anhydrous silicate melts (e.g., Kushiro
1975;Ryerson 1985;Hirschmann et al. in press), and it is
possible that H20 affects the speciation of alkalis in such
a way as to reduce this effect. It is also possible that the
higher concentrations of CO2 in our hydrous melts have
L
an effect on Yst6 , but the agreement between our results
2
and those of Kushiro (1990) argue against it being
significant.
Figure 4a and b are plots ofwt% FeO and wt% MgO
versus molar Mgj(Mg + Fe) comparing the composi-
tions of our experimentally produced hydrous and an-
hydrous silicate melts in equilibrium with a spinel
lherzolite assemblage at 1.2 GPa. As was the case with
Si02, the presence of dissolved H20 produces significant
decreases in the concentrations of both FeO and MgO.
Thermodynamic controls on the MgO and FeO contents
of hydrous peridotite partial melts can be identified by
considering the molar Olivjmelt partition coefficients for
these elements (DOlivjMelt = XOliv
jXMelt). Figure 5 con-
MO'j MO MO 'j
tains plots of (a) log D~~~Meltand (b) log D~~~Meltversus
inverse temperature, showing Oliv-melt pairs from both
anhydrous and H20-bearing experiments performed at
pressures of 0.9 to 2.0 GPa and temperatures of 1170 to
1370 "C. The hydrous and anhydrous experiments fall
along the same trend for the partitioning of both FeO and
MgO between Oliv and liquid. This suggests that the
dominant control on the FeO and MgO contents of these
melts is temperature, and that because hydrous melts are
in equilibrium with olivine of a given composition at sig-
nificantly lower temperatures than anhydrous melts, their
Olivjsilicate melt partition coefficientsare larger and they
have lower FeO and MgO contents.
The relative importance of temperature versus dis-
solved H20 in controlling the FeO and MgO contents of
peridotite partial melts can be quantified by considering
a formation reaction of the form:
2
336

0.80

0.30 o Hydrous Melts (This Study)

P=0.9 -2.0 GPa
• Anhydrous Melts (This Study;
Kinzler & Grove, 1992) -¢- 0.70

0; 0.20 ~
~ a
B ~ o
~ 0
~0.60
0010
o
Ol . Ol
.Q ..Q

0.50
0.00

0.40
®
-0.10
6.0 6.2 6.4 6.6 6.8 7.0 6.0 6.2 6.4 6.6 6.8 7.0
1O,OOOfT (K) 10,000fT (K)

Fig. Sa, b Plots of: a log D~~~/Melt; b log D~i~Melt versus inverse
temperature comparing nominally anhydrous (/!tIed circles) and H20-
Si02 calculations, which show that varies stronglyY~:62
as a function of the concentration of dissolved H20, the
bearing (open circles) silicate melts saturated with a mantle peridotite
mineral assemblage of Oliv + Opx ± Cpx ± Plag ± Sp ± Gt. calculations for MgO indicate that the dominant control
Experimental conditions are pressures of 0.9-2.0 GPa and tempera- on Y~io
is temperature. If any dependence of on Y~io
tures of 1170-1370 DC.Data are from this study and from Kinzler and
Grove (1992a). Partition coefficients were calculated on a molar basis
-1.5
using the liquid components of Bottinga and Weill (1972), with all
H20 treated as molecular H20. The data from Kinzler and Grove
(1992a) included in this comparison are limited to experimentally o Hydrous Melts (This Study)
produced liquids with Na20 contents (1.35-3.87 wt%) similar to • Anhydrous Melts (This Study;
those of the silicate liquids produced in this study (1.94-3.59 wt%).
Kinzler & Grove, 1992)
The experiments of Kinzler and Grove (1992a) with anomalously low
Olivjmelt exchange K~e/Mg values (:0:0.26) have been excluded.
(Vertical error bars 2IT values calculated by propagating the standard
deviation of the mean for FeO and MgO values from Tables 3 and 5,
horizontal error bars ± 10 DC for experiments from this study and
~o
± 15 DCfor experiments from Kinzler and Grove 1992a). Where error :3" ~ -2.5
bars are not shown, they are smaller than symbols <-
.£:

where Mis Mg or Fe. Longhi et al. (1978) showed that

the equilibrium constant for this reaction (Keq) can be
rearranged to give the molar Oliv/melt partition coeffi-
cients for MgO and FeO:
X01iv 1/2 Liq
DOliv/Melt= MO = 0.667(K aLiq) ~ 3
MO XLiq eq S102 y -3.5
MO MSio,S02
6.0 6.2 6.4 6.6 6.8 7.0
where Xko is the mole fraction of either FeO or MgO in
Oliv or silicate melt, and MSio.s02 is either forsterite or 10,OOOfT (K)

fayalite. Equation 3 shows that the FeO and MgO

Fig. 6 Plot illustrating the relationship between In Y~io' calculated as
contents of a silicate melt in equilibrium with mantle discussed in the text, and inverse temperature for nominally
olivine of a given composition will be dependent on Keq, anhydrous (filled circles) and H20-bearing (open circles) silicate melts
on a~:6'and on the ratio of the activity coefficients for saturated with a mantle peridotite mineral assemblage (Oli-
2
FeO or MgO in the liquid and for fai;alite or forsterite in v + Opx ± Cpx ± Plag ± Sp ± Gt) at 0.9-2.0 Gpa and 1170-
1370 DC.Data are the same as in Fig. 5 and are from this study and
the Olivo Of these variables, only y~'b
could directly be from Kinzler and Grove (1992a). The standard state free energy of
affected by the presence of H20 dissolved in a melt in pure MgO liquid at the pressure and temperature of interest was
equilibrium with a mantle peridotite mineral assem- determined by first calculating the Gibbs free energy of periclase at its
blage. 0.1 MPa melting point (3105 K) using thermochemical data from
Berman (1988). The Gibbs free energy of pure MgO liquid at the
In the same way that Eq. I was used to calculate
Liq h . pressure and temperature of interest was then calculated using the
y Si02' t e reaction: enthalpy of fusion and heat capacity from the JANAF tables (Chase
Mg2SiO~liv = 1Mg2Si20~PX + MgOLiq 4 et al. 1985). Due of the lack of volume data for molten MgO, the
following values were adapted on the basis of the results of Cohen and
was used to calculate the activity coefficient for MgO Gong (1994), Lange and Carmichael (1987), and Kress and
Carmichael (1991): V = 1.626 Jjbar at 0.1 MPa and 3105 K;
(y~io) in each of the experimentally produced liquids dV/dT = 2.62 x 10-4 Jjbar K; dV/dP = -2.00 x 10-6 Jjbar2 at
shown in Fig. 5. The results from these calculations are 1673 K; (dV/dP)/dT = -1.30 x 10-8 Jjbar2 K. The heat capacity
shown in Fig. 6. In contrast with the results from the of molten MgO was assumed to be independent of temperature
 337

Table 8 Anhydrous basis comparison of variations in spinel lher- with increasing pressure under anhydrous conditions
zolite-saturated melt compositions as a function of varying pressure and at a constant concentration of H20 dissolved in the
and dissolved H20. (I increases, D decreases, C constant)
melt. From the systematics presented in Table 8 it is
Oxide Constant F Constant MgO evident that, at a given extent of partial melting, in-
creasing the amount of H20 dissolved in the melt at a
Increasing H20 at constant P single pressure, and increasing the pressure at which
Si02 I I
Al203 I I
melting occurs under anhydrous conditions have oppo-
FeO D D site effects on normalized melt compositions. The ap-
MgO D parent composition of a hydrous partial melt formed at
CaO C I 1.6 GPa is nearly the same as that of an anhydrous
Na20 C D
Increasing P at constant H2O
partial melt formed at 1.2 GPa. Kushiro (1990) reached
Si02 D D a similar conclusion on the basis of basalt-peridotite
Al203 C I sandwich experiments.
FeO I I Figure 7 contains plots of wt% Si02 versus total
MgO I FeO + MgO, in wt%, comparing the compositions of
CaO C D
Na20 C I hydrous and anhydrous 1.2 GPa spinel lherzolite-satu-
Increasing P, anhydrous" rated melts with H20 included in the compositions
Si02 D D (Fig. 7a), and on an anhydrous basis (Fig. 7b). When
Al203 D C H20 is included in the composition there is a positive
FeO I I
MgO I correlation between Si02 and total FeO + MgO. This
CaO C D trend is opposite to that expected from an expansion of
Na20 C I the Oliv stability volume, as shown by the FOs9 Oliv
control line in Fig 7a. When the melt compositions are
"Determined on the basis of comparison of batch melt composi-
tions calculated using the method of Kinzler (1997) normalized on an anhydrous basis, however, the ele-
vated Si02/(MgO + FeO) ratio of the hydrous melts
produces an apparent expansion of the Oliv stability
dissolved H20 exists, it is negligible. Therefore, tem- field, as illustrated by the relative positions of hydrous
perature represents the dominant control on the MgO, and anhydrous melt compositions along the FOs9 Oliv
and by analogy FeO, contents of moderate extent an- control line shown in Fig. 7b. This is also seen in nor-
hydrous and hydrous peridotite partial melts. The dif- mative projection schemes, such as that shown in Fig. 8.
ference in the mixing behaviors of Si02 and MgO with The lowest normative Oliv is found in the melt produced
respect to H20 is plausibly related to the role of the
former as a network former and of the latter as a net-
work modifier in silicate melts. Fig. 7a, b Plot of the weight concentration of Si02 versus total
Having identified some of the important thermody- weight concentration of FeO + MgO, comparing experimentally
namic controls on the compositions of H20-bearing produced anhydrous (filled symbols) and hydrous (open symbols)
silicate melts saturated with a spinel lherzolite assemblage at 1.2 GPa
peridotite melts, we now examine their compositional and 1185-1345 DC: a with H20 included in the composition; b on a
systematics using liquid compositions that have been volatile-free basis. Solid line illustrates the effect of addition or
normalized to 100% on a volatile-free basis. The ap- subtraction of F089 Oliv from the volatile-free composition of the
parent compositional variations in lherzolite-saturated liquid from experiment B303. Experiments performed using mixtures
of 82-72f basalt and PUM peridotite are represented by circles.
melts as a function of H20 content are summarized in Experiment performed using a mixture of DM151 basalt analog and
Table 8 and in Figs. 7 and 8. For comparison, Table 8 PUM peridotite is represented by a triangle. Error bars are lIT from
also lists the melt compositional variations associated Tables 3 and 5

21 21
~ Comparison of 1.2GPa Comparison of 1.2 GPa
~
!.
0 Melt Compositions 'l
!. Melt ComJr0sitions +
-
iii
:2
20

19
on a Hydrous Basi~

Anhydrous
-
iii
:2
20

19
n an Anhy reus Basis
Anhydrous
.S! .S!
g 18 + g
i:75 i:75 18
.s -9-+ .s
0 17 0 17
Ol
:2 i 3.3 -6.3 wt% Ol
:2
+ H20 F089 Olivine +
16 16
0
(])
LL
® + Control Line 0
(])
LL @
15 15
44 45 46 47 48 49 44 45 46 47 48 49
Si02 in Silicate Melt (wt'%) Si02 in Silicate Melt (wt%)
338
Cpx Cpxso
PlagA o1"
Projected From
Si02 and H20
(Oxygen Units)
Melts Saturated With
Oliv + Opx + Cpx + Sp
at 1.2 GPa
3.3 to 6.3 wt% ~
H20 A.
o
crAnhydrous
Plag Olivso
Fig. 8 Pseudoternary projection from Si02 and H20 onto the Plag-
Cpx-Oliv plane comparing the compositions of nominally anhydrous
(filled symbols) and H20-bearing (open symbols) experimentally
produced silicate liquids saturated with a spinel lherzolite assemblage
at 1.2 GPa and 1185-1345 "C. Experiments performed using mixtures
of 82-72f basalt and PUM peridotite are represented by circles.
Experiment performed using a mixture of DM151 basalt analog and
PUM peridotite is represented by a triangle. Projection scheme is from
Tormey et al. (1987)
in the experiment performed using the synthetic basalt
(DM151) with a higher total alkali content (open tri-
angle). Once again it is evident that the change in the
apparent composition of lherzolite-saturated silicate
melts associated with increasing dissolved H20 is the
same as that associated with decreasing pressure.
Our experimental results indicate that the apparent
increase in partial melt Si02 content associated with 3.3-
6.3 wt% H20 is only ~1 wt%, significantly less than
would be necessary to produce andesitic magmas di-
rectly from partial melting of hydrous mantle peridotite.
A similar conclusion can be drawn from an examination
of the liquid compositions produced in the hydrous
basalt-peridotite sandwich experiments of Kushiro
(1990), although the apparent Si02 contents of Ku-
shiro's 1.2 GPa melts (~50-51 wt%) are systematically
higher than ours (~48-49 wt%) at comparable H20
contents. The apparent compositions of hydrous
lherzolite-saturated melts produced at 1.0 GPa by Hi-
rose and Kawamoto (1995) are also basaltic (~50-
53 wt% Si02), with higher Si02 occurring in the more
sodic melts. Recent experimental studies are, therefore,
consistent with the idea that the material added to the
crust through subduction zone magmatism is domi-
nantly basaltic in composition (Grove and Kinzler
1986). The one exception to this is the recent study of
Hirose (1997), in which normalized hydrous melt com-
positions contain ~54-60 wt% Si02. Despite compara-
ble concentrations of alkalis and dissolved H20, the
melts produced in our experiments have apparent Si02
concentrations that are ~6-7 wt% lower than an H20-
undersaturated melt composition (54.4 wt% Si02;
~6.3 wt% H20) reported by Hirose (1997). When cor-
rected to an intermediate temperature (1198 "C), the
Y~:62value calculated for this melt composition is ~20%
lower than expected on the basis of the combined ex-
perimental database presented in Fig. 3b. Although the
experiments of Hirose (1997) were performed at 1.0 GPa
and those in Fig. 3b were carried out at 1.2 GPa, a de-
crease in pressure should produce an increase in Y~:62'
The elevated Si02 contents reported by Hirose (1997),
therefore, do not appear to be consistent with our ex-
perimental results or those of Kushiro (1990), and the
reason for this discrepancy is unknown.
Peridotite melting reactions under hydrous conditions
A quantitative understanding of the stoichiometry of
peridotite melting reactions can be used to place limits
on the compositions of partial melts and their mantle
residues (Kinzler and Grove 1992a), on the behavior of
trace elements during partial melting (Walter et al.
1995), and on the modal mineralogy of partial melting
residues (Kinzler et al. 1993). The stoichiometries of
anhydrous peridotite melting reactions have been de-
termined in several experimental studies (Kinzler and
Grove 1992a; Walter and Presnall 1994; Baker and
Stolper 1994; Walter et al. 1995; Kinzler 1997). Our
experiments illustrate the important control exercised by
the presence of dissolved H20 on the stoichiometries of
peridotite melting reactions.
Melting of anhydrous spinel lherzolite at moderate
pressures (~1.0 to 1.7 GPa) occurs through a peritectic
reaction in which Cpx, Opx, and Sp are consumed to
produce melt + Oliv (e.g., Kinzler and Grove 1992a;
Baker and Stolper 1994).At higher pressures, changes in
the compositions of coexisting Cpx and melt lead to
progressive changes in the reaction stoichiometry (Stol-
per 1980). First, at pressures of ~1.7 to 2.0 GPa, Opx
switches from being consumed during lherzolite melting
to being produced. At still higher pressures Oliv, Cpx,
and Sp are consumed during anhydrous peridotite
melting, producing melt + Opx (Kinzler 1997).
The experimentally determined stoichiometric coeffi-
cients for spinel lherzolite melting reactions under hy-
drous and anhydrous conditions are compared in
Table 9. High-Ca clinopyroxene dominates the mass of
material entering the melt under anhydrous conditions
at 1.0 and 1.2 GPa. The spinel lherzolite melting reac-
tions determined at 1.0 to 1.2 GPa from our experiments
and from those of Hirose and Kawamoto (1995) indicate
that under hydrous conditions the proportion of Opx
entering the melt increases relative to Cpx. Figure 9a
and b provide a graphical representation of this through
the use of pseudo-ternary projections from Sp onto the
Oliv - Cpx - Si02 plane. The 1.2 GPa spinel lherzolite
melting reaction is represented by a tie-line connecting
the compositions of Oliv and silicate melt that pierces a
compositional plane defined by Cpx, Opx, and Sp. The
location of the piercing point relative to the apices of
this compositional triangle represents the relative pro-
 339

Table 9 Comparison of experimentally determined stoichiometric calculated in this study were determined by propagating the stan-
coefficients for spinel lherzolite melting reactions under anhydrous dard errors from the mass balance results reported in Table 2
and hydrous conditions. Uncertainties reported for coefficients

Experiments P !1T XCpx XOpx XOliv XSp

(GPa) (DC)

Anhydrous
20_24a,c 1.0 1270-1330 0.71(5) 0.38(5) -0.22(6) 0.13(1)
B30-B52b,d 1.2 1300-1315 1.08(7) 0.17(10) -0.36(4) 0.07(2)
H179-H200b,d 1.6 1320-1340 1.34(2) -0.15(1 ) -0.25(2) 0.07(1)
Ll16- Ll20a,e 1.9 1401-1416 1.16(11 ) -0.38(5) 0.14(3) 0.09(3)
Hydrous
38-41 a.f 1.0 1200-1300 0.64(5) 0.50(11) -0.16(8) 0.02(3)
B329-B330a,g 1.2 1185-1200 0.62(9) 0.51(14) -0.25(9) 0.12(3)

a Coefficients determined using change in phase proportions "Kinzicr (1997)

b Coefficients estimated using 2 liquid method f Coefficients calculated from phase compositions reported by
c Baker and Stolper (1994) Hirose and Kawamoto (1995)
dKinzler and Grove (1992a) gThis study

portions of Cpx, Opx, and Sp involved in the melting
reaction. The compositional differences between Cpx
and Opx coexisting across the two-pyroxene phase re-
gion under hydrous and anhydrous conditions produces
a shift of the Oliv-melt tie-line piercing point away from
the Cpx apex, decreasing the proportion of Cpx entering
the melt. The stoichiometric coefficients for Cpx and
Opx in the hydrous spinel lherzolite melting reactions
are sub-equal (Table 9). This change is in response to the
lower temperatures at which hydrous peridotite melting
takes place relative to anhydrous melting. The effects of
temperature on the compositions of Cpx and Opx co-
existing across the pyroxene two-phase region are illus-
trated in Fig. 9c, where pyroxene compositions from an
anhydrous experiment performed at 1.2 GPa and
1315 °C are compared with those from experiments
performed at 1.2 GPa and 1200 °C in which the melt
contained 5.06 ± 0.04 wt% H20, and at 1.2 GPa and
1115 °C with ~12 wt% H20 dissolved in the melt. At
lower temperatures the pyroxene two-phase region is
wider, the CaO content of the Cpx is greater, and the
Opx is less calcic, changing the stoichiometry of the
spinel lherzolite melting reaction.
At 1.6 GPa, anhydrous, the compositions of coexisting
Cpx and melt are such that Opx is beginning to appear on
the product side of the melting reaction (Table 9). Our
experimental results indicate that under hydrous condi-
tions the Cpx is more calcic and the nature of the melting
reaction is the same as that determined at 1.2 GPa (i.e.,
only Oliv + liquid are produced), although the Cpx co-
efficient is larger at 1.6 GPa. At 2.0 GPa and 1275-
1290 °C, the hydrous melting experiments produced sili-
cate melts saturated with a Gt lherzolite assemblage. The
inferred hydrous peridotite melting reaction at this pres-
sure is one in which Cpx + Opx + Gt react to produce
Oliv + melt. This differs from the anhydrous Gt lherzo-
lite melting reaction determined by Kinzler (1997) at
2.3 GPa and 1430-1440 °C, in which Cpx + Oliv + Gt
react to produce Opx + melt.
Two of the hydrous melting experiments performed
at 1.6 GPa produced silicate melts in equilibrium with a
lherzolite assemblage in which Sp and Gt coexist. These
experiments allow the nature of hydrous peridotite
Fig. 9a-e Pseudoternary projections from Sp onto the Oliv-Cpx-Sit),
plane illustrating the stoichiometry of spinel lherzolite melting
reactions at 1.2 GPa under: a hydrous; b anhydrous conditions; and
c the systematic change in the compositions of experimentally
produced pyroxenes with increasing H20 dissolved in the silicate
melt and decreasing temperature. The experiment at 1315 DC is
nominally anhydrous, while the experiment at 1200 DC has
5.06 ± 0.4 wt% H20 dissolved in the melt, and the experiment at
1100 DChas ~ 12 wt% H20 dissolved in the melt. Projection scheme is
from Kinzler (1997)

Cpx Cpx Cpx

/\ 1115DC
/ ~~200DC
C px \ Projected From
D
Spinel
1315 C (Oxygen Units)

Effect of T
on Pyroxene
Compositions
Oliv Opx
340
melting reactions at pressures corresponding with the
spinel to garnet transition to be inferred. Such a
lherzolite melting reaction, involving both Sp and Gt, is
shown schematically in Fig. 10. The phases entering the
melt are represented by filled circles, while the open
circles are the phases being produced. The coexistence of
Sp and Gt produces a compositional tetrahedron with
the Cpx-Opx-Sp plane as its base and Gt as its apex. The
point at which the Oliv-melt tie-line pierces the base of
the tetrahedron defines a Sp-lherzolite melting reaction
similar to those listed in Table 9. The point at which the
Oliv-melt tie-line pierces Cpx-Opx-Gt compositional
plane defines a Gt-lherzolite melting reaction similar to
the one described above. The overall lherzolite melting
reaction is a combination of these two reactions in which
Cpx, Opx, Sp, and Gt react to form Oliv and melt with
increasing temperature.
The spinel to garnet transition
The pressure at which ascending mantle peridotite that is
at or above its solidus intersects the Sp to Gt transition
influences both the major and trace element composi-
tions of partial melts by controlling the amount of
melting that occurs within the Gt stability field (Kay and
Gast 1973; Salters and Hart 1989; Kinzler 1997). The
pressure of intersection of the anhydrous peridotite
solidus with the Sp to Gt transition is poorly constrained
by existing experimental data, but has been estimated to
be ~2.5 GPa (Hirschmann and Stolper 1996). Because
of the pressure-temperature dependence of the transi-
tion, Gt should be stable to lower pressures in tectonic
environments where the mantle potential temperature is
relatively low, such as subduction zones. Given the sol-
idus-lowering effect of H20 on mantle peridotite, it is
likely that the amount of melting that occurs within the
Hydrous Sp + Gt
Lherzolite Melting
at 1.6 GPa
Oliv
Fig. 10 Schematic illustration of melting reaction for hydrous
peridotite containing coexisting Sp and Gt at 1.6 GPa. Filled circles
are solid phases being consumed during melting and open circles are
phases being produced. Lightly-shaded triangle is compositional plane
formed by coexisting Cpx + Opx + Sp. Darkly-shaded triangle is
compositional plane formed by coexisting Cpx + Opx + Gt
Gt stability field is greater in subduction zones than it is
beneath mid-ocean ridges. Our experimental results
provide an estimate of the magnitude of this effect.
A comparison of the mineral assemblages in our hy-
drous and anhydrous experiments shows that, for a
constant silicate bulk composition, Gt joins the mantle
residual assemblage at a lower pressure under hydrous
conditions. Spinel and Gt coexist at 1.6 GPa and 1255-
1260 °C in hydrous experiments, while only Sp occurs at
1.6 GPa and 1355-1370 °C under anhydrous conditions.
Garnet is the stable aluminous phase in the hydrous
experiments performed at 2.0 GPa and l275-1290°C.
Although the relative stabilities of Sp and Gt are sensi-
tive to the Cr content of Sp and the Fe content of the
minerals (O'Neill 1981), the compositional similarities
between the phases in the hydrous and anhydrous
1.6 GPa experiments suggest that temperature is the
important variable in this case. This possibility was in-
vestigated using the results of Kinzler (1997), who per-
formed melting experiments on bulk compositions
similar to ours (i.e., intermediate to basalt and perido-
tite) and found that Gt and Sp coexist with Oliv, Cpx,
Opx, and anhydrous silicate melt at 1.9 GPa and
1396 0C. Extrapolating this to 1.6 GPa using the dTjdP
slope for the Sp to Gt transition in natural peridotite
(~500 °CjGPa) (O'Hara et al. 1971)gives a temperature
of 1246 °C, in reasonable agreement with our experi-
mental conditions (1255-1260 0C). Although it is pos-
sible that at a given temperature the Sp to Gt transition
occurs at a higher pressure for a peridotite bulk com-
position than in experiments such as ours, the solidus-
lowering effect of H20 will stabilize Gt in the melting
regime to pressures that are several hundred MPa lower
than under anhydrous conditions.
Isobaric batch melting of hydrous mantle peridotite
Various subduction zone thermal models have been
proposed, and although they all predict a downward
deflection of mantle isotherms in the vicinity of the slab,
model mantle wedge temperatures are strongly depen-
dent on assumed heat sources and sinks (McKenzie
1969; Oxburgh and Turcotte 1970; Toksoz et al. 1971;
Anderson et al. 1976; Davies and Stevenson 1992). In-
dependent estimates of temperatures in the mantle
wedge from experimental studies of primitive arc basalts
are much higher than those predicted by thermal mod-
els, even if the effects of H20 are taken into account
(e.g., Tatsumi et al. 1983; Baker et al. 1994). A quanti-
tative understanding of the influence of H20 on melt
generation has the potential to place new constraints on
models of the dynamics of subduction zones and to
reconcile petrologic observations with subduction zone
thermal models. Although melting of anhydrous mantle
peridotite beneath mid-ocean ridges is thought to be a
polybaric, near-fractional process (e.g., Klein and Lan-
gmuir 1987;Johnson et al. 1990),isobaric batch melting
of hydrous mantle peridotite provides basic insights into

melt generation processes at subduction zones. Here we
investigate the effects of H20 on the temperature at
which batch melts coexist with mantle peridotite at
1.5 GPa, on isobaric melt production rates, and on the
extent to which peridotite partially melts at a given
pressure and temperature. . Anhydrous
Taking advantage of the observation that y~io
directly affected by the presence of dissolved H20, we
is not
developed an approach to modeling the liquidus tem-
peratures of isobaric batch melts of hydrous mantle
peridotite using the Oliv/melt partitioning of MgO. This
approach allowed us to exploit an extended database of
experimentally produced Oliv-saturated melt composi-
tions from the literature consisting of 69 hydrous and 65
anhydrous melts coexisting with olivine at temperatures
of 940 to 1511 °C, and pressures of 0.1 MPa to 2.3 GPa
(Kinzler and Grove 1992a; Sisson and Grove 1993a,b;
Gaetani et al. 1994; Hirose and Kawamoto 1995; Wag-
ner et al. 1995; Kinzler 1997; Grove et al. 1997). The
concentrations of K20 (0.04-2.04 wt%) and of Na20
(0.78-4.7 wt%) in the hydrous melts are broad enough
to allow meaningful liquidus temperature calculations to
be carried out for low extent partial melts. Details of the
calculation procedure are presented in an appendix.
The results from liquidus temperature calculations
for an anhydrous peridotite (solid curve), for a peridotite
containing 0.15 wt% H20 (dashed curve), and for a
peridotite containing 0.32 wt% of an H20-Na20-K20
subduction component (SC) (dotted curve) are shown in
Fig. 11. The peridotite composition used in these cal-
culations is the depleted MORB source of Kinzler
(1997), and the SC composition was derived from the
H20-rich Mariana component of Stolper and Newman
(1994) by normalizing the concentrations of H20, Na20,
and K20 to 100%. The liquidus temperatures of the
anhydrous partial melts increase systematically from
1330 °C at 2% partial melting to 1400 °C at 20%, de-
fining a temperature-melt fraction (T-F) curve that is
concave-downward. The temperature of the H20-bear-
ing peridotite must be raised by ~120 °C, and that of the
SC-bearing peridotite by ~200 °C, in order to increase
the extent of partial melting from 2 to 5%. These tem-
perature increases are ~4-7 times larger than is required
in the anhydrous case (~30 0C) and result primarily
from a dilution of the concentration of H20 dissolved in
the melt with increasing extent of partial melting. In-
creasing the partial melting from 5 to 20% for the H20-
bearing peridotite requires that the temperature be
raised by ~90 °C and that of the SC-bearing peridotite
be raised by ~ 130°C, while the temperature increase
required under anhydrous conditions is only ~40 "C.
The large temperature increases required to partially
melt H20- and SC-bearing peridotite are a reflection of
their relative isobaric melt production rates, (oF joT)p,
or the change in melt fraction for a given change in
temperature. Isobaric batch melting rates were calcu-
lated for each of the T- F curves in Fig. 11 and are shown
in Fig. l2a and b, plots of log(oF joT)p versus F and of
log(oF joT)p versus temperature. For the anhydrous
341
Forsterite in Olivine (Mole%)
89 90 91
1500
1400
Peridotite
--
f) 1300
/
/ Peridotite +
0.15wt% Hp
/ ,:
Peridotite + 0.32 wt%
1100 Mariana Subduction
Component
1000
o 0.05 0.10 0.15 0.20
Melt Fraction
Fig. 11 Plot of melt fraction versus temperature comparing the
liquidus temperatures of anhydrous batch melts of a depleted MORB
mantle source at 1.5 GPa (solid curve) calculated using the methods of
Kinzler (1997) with the liquidus temperatures of hydrous batch melts
from peridotite containing 0.15 wt% H20 (dashed curve) and
0.32 wt% of simplified Mariana subduction component (dotted
curve). Liquidus curves for H20-bearing batch melts were calculated
as described in the text
peridotite, the isobaric melt production rate is 0.05%;oC
at 2% partial melting and increases continuously with
increasing extent of melting to 0.8%;oC at 20% partial
melting. The H20-bearing peridotite has a (oF joT)p at
2% partial melting (0.01%;oC) that is a factor of 5 lower
than the anhydrous case, while the melt production rate
for the SC-bearing peridotite (0.007%;oC) is lower by a
factor of 7. The melt production rates for both the H20-
and SC-bearing peridotites increase faster as functions
of F than the anhydrous case, so that at 20% partial
melting they differ from the anhydrous (oF joT)p by
approximately a factor of 2. If (oF joT)p is considered as
a function of temperature, the melt production rates for
the H20- and SC-bearing peridotites are higher than for
the anhydrous peridotite at a given temperature
(Fig. l2b). This is due to the increase in (oF joT)p with
increasing F, and reflects the increased extent of melting
for the H20- and SC-bearing peridotites at a given
temperature relative to the anhydrous peridotite.
Asimow et al. (1997) showed that the most significant
factors for controlling the polybaric melt production
rate during isentropic (adiabatic) ascent of mantle
peridotite are the isobaric productivity, (oF joT)p, and
the pressure-temperature slopes of constant melt frac-
tion contours, (oT joP)F' We calculated (oT joP)F values
at 1.5 GPa for the 5% melt contour of anhydrous
peridotite (1.9 °C/GPa) and of peridotite containing
0.15 wt% H20 (1.6 °CjGPa), and combined them with
342
Forsterite in Olivine (Mole%)
89 90
-1
Peridotite +
0.15wt%H20
-2
LLII-'o..
~'b
~ -3
.Q
/ .:
""
'
-4
/ ...
Peridotite + 0.32 wt%
Mariana Subduction
Component
-5
®
o 0.05 0.10 0.15
Melt Fraction
Fig. 12 a Plot of 10g(aF jaT) p versus melt fraction comparing the
isobaric batch melt production rates of anhydrous peridotite (solid
curve) with peridotite containing 0.15 wt% H20 (dashed curve) and
0.32 wt% simplified Mariana subduction component (dotted curve) at
1.5 GPa. Curves were calculated by fitting a polynomial of the form
T = Lc;F±n to the temperatures from Fig. 11, taking its derivative
with respect to F, then inverting to get (aF jaT)p. b Plot of
10g(aF jaT)p versus temperature comparing the isobaric batch melt
production rates of anhydrous peridotite (solid curve) with peridotite
containing 0.15 wt% H20 (dashed curve) and 0.32 wt% simplified
Mariana subduction component (dotted curve) at 1.5 GPa
the (oF joP)p values from Fig. 12 to calculate the pro-
ductivity, (-oF joP)s, of H20-undersaturated polybaric
melting relative to anhydrous melting using the pro-
ductivity equation of Asimow et al. (1997). Thermo-
chemical and volume data for diopside were used in the
calculation (see Table 1 of Asimow et al. (1997) and
references therein); thus the absolute productivities are
approximate, but the relative values provide an estimate
of the magnitude of the effect of H20 on polybaric melt
generation rates. The results indicate that at 5% partial
melting the H20-undersaturated melting rate is ap-
proximately half that for anhydrous melting. This dif-
ference will increase at lower extents of melting and
decrease at higher melt fractions. Polybaric melt pro-
duction is, therefore, an inefficient process for closed-
system melting at fluid-undersaturated conditions. The
amount of melt that can be produced in a subduction
zone through the breakdown of amphibole followed by
adiabatic ascent of mantle peridotite is extremely limited
unless H20 is periodically added to the zone of melt
generation.
The increase in melt fraction produced by increasing
the concentration of H20 in the peridotite,
(oF jOCH20)p T' at 1.5 GPa and temperatures of 1200 to
1350 °C is shown in Fig. l3a, a plot of melt fraction
versus H20 in the peridotite. From this plot it can be
seen that (oF jOCH20)p T increases with increasing tem-
perature. For example, 'the addition of 0.25 wt% H20 to
a peridotite at 1200 °C increases the extent of melting
from 0.5 to 3%, while at 1350 °C the melt fraction in-
creases from 3 to 12%. Despite this temperature de-
91
-1
-2
Peridotite + 0.32 wt% ~'
Mariana Subduction .' ' Anhydrou~
Component . 'j Peridotite
~.,';
-4 ......... / \
Peridotite +
0.15wt%H20
-5
. ,
0.20 1000 1100 1200 1300 1400 1500
Temperature (DC)
pendence, the (oF jOCH20)P T values indicated by our
calculations are significantly lower than the value in-
ferred by Stolper and Newman (1994) from a suite of
basaltic glasses from the Mariana Trough, in which the
addition of 0.25 wt% H20 to the peridotite increases the
extent of melting by ~ 15%. The difference between our
calculations and the increase in extent of melting ob-
served in the Mariana basalts may reflect several factors.
As noted by Stolper and Newman (1994), in addition to
the effect of H20, the range of extents of melting rep-
resented by the Mariana basalts could reflect a system-
atic variation in temperature or the effect of the addition
of alkalis from the H20-rich component to the perido-
tite. We investigated the influence ofrefertilization of the
peridotite on extent of melting, and the results are shown
in Fig. l3b. At 1330 °C, the addition of any of the major
constituents of the Mariana SC (H20; K20; Na20) is
not by itself sufficientto explain the observed increase in
extent of melting. The curves in Fig. l3b show that the
addition of H20 (long dashes) has the strongest effect on
melt fraction, while the addition of K20 (short dashes)
produces a smaller melt fraction increase, and Na20
(dash-dot) has least effect on extent of melting. If,
however, a H20-K20-Na20 SC is added to the perido-
tite, the match between our calculated increase in extent
of melting (dotted curve) and that inferred by Stolper
and Newman (1994) (solid line) is very good.
There are two important conclusions concerning
subduction zone melt generation to be drawn from these
calculations. First, the Mariana basalts can be explained
by a melt generation process in which they equilibrated
with mantle peridotite at nearly identical pressure-tem-
perature conditions. We chose 1.5 GPa to carry out our
calculations because it represents a reasonable minimum
depth for melt generation in the wedge, and the results
do not place rigorous constraints on the conditions of
melt generation beneath the Mariana back arc. The
calculations do, however, indicate that the combined
effects of H20 and alkalis can account for the inferred
melting extents and that a systematic temperature in-
crease is not required. Second, the influence of the ad-
 343

0.30 ~ 0.60
Kp 0.25
I
2 I
;g
~
~
0.20
~
'1:
cf. 0.40
N~I I
I /H 20
\'330 C
P=1.5 GPa
0
0.20 !-
~
2 .!::
I
// 2
C 0.15 ~

I ////
"0
'1: (]) '1:
(]) I: Slope From (])
Q. Q.
0
0. Stolper & Newman
.s (1994) 0.10 .s
0.10 E 0.20
0 0
0 0 . I
or
:r: I:
II. : Mariana Subduction 0.05 :r:
'"
0

®
is:J I .• ' Component
@
"0
.0 0 0
0.05 0.10 0.15 ~ 0 0.05 0.10 0.15 0.20 0.25
Melt Fraction Melt Fraction

Fig. 13 a Plot of melt fraction versus H20 in peridotite showing the supplemental calculator. The first author gratefully acknowledges
relationship between these variables at temperatures of 1200-1350 DC the financial support of EM Stolper and PI Wyllie during final
and a pressure of 1.5 GPa. Curves were determined by calculating manuscript preparation. This research was supported by NSF
temperature versus melt fraction curves for peridotites containing grants EAR-9406177 and EAR-9706214, and by an O.K. Earl Prize
various amounts of H20, then determining isotherms. b Plot of melt Postdoctoral Fellowship from the Division of Geological and
fraction versus subduction component in peridotite illustrating the Planetary Sciences at the California Institute of Technology.
effects of adding H20 (dashes), Na20 (dash-dot), K20 (small dashes),
and simplified Mariana subduction component to peridotite (dots).
Curves for addition of K20 and Na20 were calculated using the
method of Kinzler (1997). Shown for comparison is the subduction Appendix
component versus melt fraction slope determined for basalts from the
Mariana back are by Stolper and Newman (1994) The temperature-melt fraction calculations presented in this paper
were carried out using expressions describing the Oliv/melt parti-
tioning of MgO:

dition of a subduction-related component to the mantle X01iv 5404 ± 139

wedge on the melt generation process will be strongly In X~i~O = 7.53 ± 0.95 + T(K)
MgO
dependent on the composition of the Sc. If it is alkali-
poor, the amount of melt produced at a given pressure - 1.76 ± 0.24 ( 1 - L' )2
XN~\I02
and temperature will be much less than would be gen-
- 8.25 ± 0.97 ( 1 - XKL' )2
;(I02 Al
erated by the addition of a high-alkali Sc. The details of
the melt generation process may, therefore, vary from and of FeO:
arc to arc, with the composition of material transferred
from the subducted slab to the mantle wedge exercising X01iv 5559 ± 350
an important control on the amount of melt produced. In ;~~ = 7.29 ± 1.26 + T(K)
FeO
(P(bars) - 1)
Acknowledgments The authors would like to thank M. Hirschmann + 0.017 ± 0.006 T(K)
and T. Sisson for thoughtful and constructive reviews. We are also
grateful to S. Bowring, F. Frey, P. Hess, and G. Hirth for com-
ments on an earlier version of the paper, and to M. Baker, I. Eiler, - 0.95 ± 0.29 ( 1 - L' )2
XN~\I02
M. Hirschmann, G. Hirth, R. Kinzler, S. Newman, and T. Sisson
for helpful discussions. We would like to thank 1. Kushiro for - 10.09 ± (
1.20 1 -
L,)2
X ;(I02 A2
K
generously providing unpublished experimental data. N. Chatterjee
and M. Iercinovic kept the electron microprobe facility at MIT that were calibrated by performing stepwise multiple linear re-
running smoothly over the course of this study. We are grateful to gressions to determine the significant variables (regression param-
S. Newman for performing the FTIR analyses, and to A. Kent for eter uncertainties are 10} Melt compositions in the calibration
performing the ion probe analyses. M. Ghiorso provided advice on database were recalculated, on a molar basis, into the components
calculating Si02 activities, and timely assistance with the MELTS of Bottinga and Weill (1972), molecular H20, and molecular CO2,

Table Al Mineral/melt partition coefficients and weight-to-molar study; other partition coefficients are from Kinzler and Grove
conversion factors used in liquidus temperature calculations. Cpx/ (1992a). (CH20 weight concentration of H20 in silicate melt, XH20
melt and Opx/melt partition coefficients for Na20 are from this molar concentration of H20 in silicate melt)

Mineral/melt partition coefficients

Cpx Opx Oliv Sp
0.25 0.031 0.001 0.001
0.001 0.001 0.001 0.001
Weight percent-to-mole fraction conversion factors
H20 Na20 K20
0.037-0.0009CH20 0.022-0.017XH2o 0.014-0.011XH2o
344
Equation Al has an r2 value of 0.98 and, when rearranged to
predict temperature, recovers the calibration database with a mean
uncertainty of ± 24°C. Equation Al predicts the liquidus tem-
peratures for the experimentally produced anhydrous spinel
lherzolite partial melts of Baker and Stolper q994) with a mean
uncertainty of ± 20°C. Equation A2 has an r value of 0.96 and
recovers the Oliv /melt partition coefficients in the calibration da-
tabase with a mean uncertainty of ± 7% relative.
Calculating the liquidus temperatures of hydrous peridotite
partial melts using Eq. Al requires knowledge of the equilibrium
olivine composition, and the molar MgO, NaAI02, and KAI02
contents of the melt. Equilibrium Oliv compositions were determined
by first calculating, at 1% intervals using the methods of Kinzler
(1997), the compositions and liquidus temperatures of anhydrous
batch melts, ranging from 2 to 20% partial melting, generated at
1.5 GPa from a depleted MORB source. Equations Al and A2 were
then used to calculate the compositions of Oliv in equilibrium with
each of these melts (F089.1-91.1). Because H20 dissolved in the melt
does not have a significant effect on the Oliv /melt exchange K~e/Mg,it
was assumed that the variation in Oliv composition as a function of
extent of partial melting is identical for both hydrous and anhydrous
peridotite melting. The large proportion of olivine in spinel lherzolite
(~50 wt%) buffers its composition, so that the composition of oli-
vine in hydrous and anhydrous peridotite should not be significantly
different between 2 and 20% partial melting.
The mole fraction of MgO in a given H20-bearing partial melt
was estimated from the MgO content of the anhydrous melt in
equilibrium with the same Oliv using the approximation:
xHydrousLiq "'" (1 _ xHydrousLiq) XAnhdrousLiq
A3
MgO - H20 X MgO
When Eq. Al and A3 are used to calculate the liquidus tempera-
tures for the H20-bearing melts from experiments B304, B330, and
B359 from the MgO contents of the anhydrous melts from Ex-
periments B303, B287, B394, the calculated temperatures are in
good agreement with the measured temperatures (1219 °C versus
1215 DC; 1225 °C versus 1200 DC; 1267 °C versus 1260 0C). The
Na20, and K20 contents of the hydrous partial melts were calcu-
lated using the batch melting equation and mineral/melt partition
coefficients given in Table AI. Weight concentrations of H20,
Na20, and K20 were converted to molar concentrations using
conversion factors determined on the basis of regressions of our
experimental database (Table AI). Water was assumed to behave
as a perfectly incompatible element during partial melting.
The melting of amphibole lherzolite under fluid-absent condi-
tions could not rigorously be incorporated into our calculations due
to the lack of experimental data on natural compositions. The
maximum stability of pargasitic amphibole, and thus the maximum
temperature at which it will be lost during partial melting, was es-
timated from the experimental results of Holloway (1973). The
maximum stability of amphibole occurs when the H20 content of
the coexisting melt is ~0.5 times the saturation value, or ~ 7-8 wt%
at 1.5 GPa. The maximum temperature stability for endmember
pargasite at 1.5 GPa is ~ 1125 "C. We estimate, therefore, that
amphibole will be exhausted by ~ 1-2% partial melting for the bulk
compositions that we investigated, and calculations were begun at
2% partial melting. Amphibole-bearing peridotite melts by a reac-
tion in which amphibole and Opx are consumed to produce liquid,
Cpx, Oliv, and Sp (Sisson et al. 1997). Because this reaction will
produce only ~1-2% melt in the bulk compositions investigated,
the presence of amphibole at the solidus should not have a signifi-
cant effect on the residual mode relative to melting of spinel
peridotite.
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