Earth and Planetary Science Letters 355-356 (2012) 327340

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Earth and Planetary Science Letters

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Partitioning of V, Mn, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb,
and Bi between sulde phases and hydrous basanite melt
at upper mantle conditions
Yuan Li n, Andreas Audetat
Bayerisches Geoinstitut, Universit
at Bayreuth, 95440 Bayreuth, Germany

a r t i c l e i n f o

abstract

Article history:
Received 15 December 2011
Received in revised form
5 July 2012
Accepted 8 August 2012
Editor: T. Elliot
Available online 26 October 2012

The partitioning of 15 major to trace metals between monosulde solid solution (MSS), sulde liquid
(SL) and mac silicate melt (SM) was determined in piston-cylinder experiments performed at 1175
1300 1C, 1.53.0 GPa and oxygen fugacities ranging from 3.1 log units below to 1.0 log units above the
quartzfayalitemagnetite fO2 buffer, which conditions are representative of partial melting in the
upper mantle in different tectonic settings. The silicate melt was produced by partial melting of a
natural, amphibole-rich mantle source rock, resulting in hydrous (B5 wt% H2O) basanitic melts similar
to low-degree partial melts of metasomatized mantle, whereas the major element composition of the
starting sulde (B52 wt% Fe; 39 wt% S; 7 wt% Ni; 2 wt% Cu) was similar to the average composition of
suldes in this environment. SL/SM partition coefcients are high (Z 100) for Au, Ni, Cu, Ag, Bi,
intermediate (1100) for Co, Pb, Sn, Sb (7 As, Mo), and low (r 1) for the remaining elements. MSS/SM
partition coefcients are generally lower than SL/SM partition coefcients and are high (Z 100) for Ni,
Cu, Au, intermediate (1100) for Co, Ag ( 7Bi, Mo), and low (r 1) for the remaining elements. Most
suldesilicate melt partition coefcients vary as a function of fO2, with Mo, Bi, As (7 W) varying by a
factor 4 10 over the investigated fO2 range, Sb, Ag, Sn (7 V) varying by a factor of 310, and Pb, Cu, Ni,
Co, Au, Zn, Mn varying by a factor of 310. The partitioning data were used to model the behavior of Cu,
Au, Ag, and Bi during partial melting of upper mantle and during fractional crystallization of primitive
MORB and arc magmas. Sulde phase relationships and comparison of the modeling results with
reported Cu, Au, Ag, and Bi concentrations from MORB and arc magmas suggest that: (i) MSS is the
dominant sulde in the source region of arc magmas, and thus that Au/Cu ratios in the silicate melt and
residual suldes may decrease with increasing degree of partial melting, (ii) both MSS and sulde liquid
are precipitated during fractional crystallization of MORB, and (iii) fractional crystallization of arc
magmas is strongly dominated by MSS.
& 2012 Published by Elsevier B.V.

Keywords:
experimental
partitioning
sulde
silicate melt
upper mantle

1. Introduction
Chalcophile and siderophile elements are important tracers to
reconstruct core-formation and mantle (-crust) differentiation
processes in the Earth (e.g., Newsom et al., 1986; Yi et al., 2000;
Righter, 2003), and all form economically valuable ore deposits
(e.g., Kesler, 1994; Robb, 2005). Both chalcophile and siderophile
elements tend to partition into sulde phases relative to silicate
melt, hence suldesilicate melt partition coefcients need to be
taken into account when constraining the geochemical behavior
of these elements in magmatic systems that are sulfur-bearing.
Suldes are actually common in the upper mantle (Lorand et al.,
1989, 1990; Szabo and Bodnar, 1995; Shaw, 1997), in mid-ocean

Corresponding author. Tel.: 49 0921 553721; fax: 49 0 921 55 3769.

E-mail address: yuan.li@uni-bayreuth.de (Y. Li).

0012-821X/$ - see front matter & 2012 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.epsl.2012.08.008

ridge basalts (MORB; Mathez, 1976; Peach et al., 1990; Jenner

et al., 2010), in arc basalts (Metrich et al., 1999; de Hoog et al.,
2001; Di Muro et al., 2008), and in many intermediate and felsic
derivatives of these magmas (Jenner et al., 2010; Wallace and
Edmonds, 2011), hence in all these environments the effect of
suldesilicate melt partitioning should be considered. Studies on
mantle xenoliths and orogenic peridotites have shown that the
dominant sulde phase in the upper mantle is monosulde solid
solution (MSS) (e.g., Lorand et al., 1989, 1990; Szabo and Bodnar,
1995; Shaw, 1997), followed by Cu-rich, interstitial suldes that
are interpreted to have been introduced during periods of mantle
metasomatism (Alard et al., 2000; Lorand and Alard, 2001; Luguet
et al., 2007).
Previous experimental studies dealing with suldesilicate melt
partitioning have focused mostly on PGE and Au (Fleet et al., 1991;
Bezmen et al., 1994; Fleet et al., 1996, 1999; Crocket et al., 1997),
whereas only few data are available for V, Mn, Co, Ni, Cu, Zn, As, Mo,

n.a.
n.a.

Vanadium partition coefcient between olivine and silicate melt.

n

AG4 S02 sulde

25
1300
LY33

3.0

1175
1185
1185
1300
1200
1200
1190
1185
1185
1185
1185
1185
1185
1200
1200
1200
1200
1200
1250
LY01
LY04
LY08
LY12
LY15
LY16
LY17
LY19
LY20
LY22
LY23
LY24
LY25
LY26
LY28
LY29
LY30
LY31
LY32

MDC: modied double capsule; Cpx: clinopyroxene; Oliv: olivine or olivine capsule; Amph: amphibole; SM: silicate melt; MSS: monosulde solid solution; SL: sulde liquid; n.a: not analyzed.

n.a.
n.a.
Cpx OlivSM MSS SL
-

n.a.

 1.00
0.42
0.70
 1.00
0.10
 1.50
0.10
0.37
n.a.
n.a.
0.35
n.a.
n.a.
 2.10
0.91
0.25
 3.10
0.97
0.62
 8.45
 6.93
 6.65
 7.10
 7.10
 8.70
 7.21
 6.98
n.a.
n.a.
 7.00
n.a.
n.a.
 9.78
 6.27
 6.93
 10.28
 6.21
 5.33
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
0.0957 70.0123
n.a.
n.a.
0.163 70.004
n.a.
n.a.
0.13 7 0.03
0.28 7 0.03
0.29 7 0.02
n.a.
n.a.
n.a.
n.a.
0.22 7 0.02
n.a.
n.a.
0.21 7 0.03
n.a.
n.a.
0.05 70.01
0.29 7 0.02
0.23 7 0.02
n.a.
0.33 7 0.02
0.19 7 0.03
Cpx Amph Oliv12%SM MSS
Cpx Amph Oliv10%SM MSS SL
Cpx Amph Oliv20%SM MSS SL
SM with quenche texture SL
SM with quenche texture MSS
SM with quenche texture SL
SM with quenche texture SL MSS
Cpx Amph OlivSM MSS
Cpx Amph OlivSM MSS
Cpx Amph OlivSM MSS
Cpx Amph OlivSM MSS
Cpx Amph Oliv7%SM MSS
Cpx Amph OlivSM MSS SL
Cpx OlivSM MSS SL
Cpx OlivSM MSS SL
Cpx OlivSM MSS SL
Cpx OlivSM MSS SL
Cpx Olivanhydrite SM MSS SL
Cpx OlivSM MSS SL

Pt95Rh05 Oliv
double Pt95Rh05 Oliv
double Pt95Rh05 Oliv
double Pt95Rh05 Oliv
MDC
MDC
MDC
Pt95Rh05 Oliv
Pt95Rh05 Oliv
Pt95Rh05 Oliv
Pt95Rh05 Oliv
Pt95Rh05 Oliv
Pt95Rh05 Oliv
Pt95Rh05 graphite Oliv
double Pt95Rh05 Oliv
double Pt95Rh05 Oliv
Fe graphite Oliv
Pt95Rh05 Oliv
Pt95Rh05 Oliv
Pt95Rh05 Oliv
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde
sulde 5%CaSO4
sulde
AG4 S03
AG4 S03
AG4 S03
AG4 S03
AG4 S03
AG4 S03
AG4 S03
AG4 S03
AG4 S03
AG4 S03
AG4 S04
AG4 S02
AG4 S05
AG4 S06
AG4 S02
AG4 S06
AG4 S02
AG4 S02
AG4 S02
24
20
20
0.5
2
0.7
0.6
15
8
2
15
15
15
40
42
44
21
30
30

Capsule
Starting material
Duration (hours)
P (GPa)
T (1C)
Exp. ID

Table 1
Overview of experimental conditions and run products.

In all experiments we used a hornblende-rich, natural mantle

rock as starting material to which 58 wt% synthetic FeNiCu
sulde was added. The hornblendite stems from a hydrous vein in
 et al., 2001;
orogenic peridotite of the French Pyrenees (Fabries
for composition, see supplementary Table 1) and was kindly
provided by Sebastian Pilet, who used the same starting material
to experimentally reproduce alkaline magmas (AG4 in Pilet et al.,
2008). The major element composition of the synthetic sulde
(50.054.4 wt% Fe; 38.341.1 wt% S; 6.87.7 wt% Ni; 1.83.0 wt%
Cu; supplementary Table 1) is similar to that of typical suldes in
metasomatized lithospheric mantle, which contain 3841 wt% S,
5054 wt% Fe, B7.0 wt% Ni and 1.83.0 wt% Cu (Lorand, 1989;
Szabo and Bodnar, 1995; Shaw, 1997; Lorand and Alard, 2001).
Between 50 and 3400 ppm of Co, Ni, Cu, Zn, Mo, As, Sn, Sb, Ag, W,
Au, Pb, and Bi were added to the synthetic sulde (supplementary
Table 1). Five different sulde compositions were synthesized
from mixtures of pure metals and sulfur powder (99.99%) in
evacuated silica glass tubes at 1200 1C as follows. About 0.5 g of
the mixture was added into silica tubes of 6 mm O.D. and 3.6 mm
I.D. which had previously been sealed on one end using a
hydrogenoxygen torch. A neatly tting silica rod of 2 cm length
was then placed above the mixture to prevent loss of starting
materials during subsequent evacuation to o10  5 bar and sealing with the hydrogenoxygen torch. In order to avoid evaporation of sulfur during sealing, the sample-containing bottom of the
silica tube was cooled by wet tissues. Finished silica tubes were
put into the furnace and heated from room temperature to 600 1C
within 1 h and kept at this temperature for 2 h. Then the
temperature was increased to 1200 1C within 1 h and kept there
for another 2 h. The samples were quenched by dropping the
silica glass tubes into cold water. The run products were optically
homogeneous, showing no evidence for immiscibility at high
temperature or exsolution during the quench, and compositional
homogeneity with respect to major and trace element contents
was conrmed by electron microprobe and laser-ablation
inductively-coupled-plasma mass-spectroscopy (LA-ICP-MS).
Manganese and vanadium were introduced by the hornblendite
starting material, except for runs LY12 and LY16 to which 0.1
0.3 wt% V were added in form of V2O5.

Imposed fO2

2.1. Starting materials

1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
2.5

Quench phases

2. Experimental methods

ReReO
ReReO
FeOFe3O4
NiNiO
CoCoO
NiNiO
MnOMn3O4
ReReO
-

*Doliv/SM
V

logfO2

DFMQ

logfS2

Ag, Sn, Sb, W, Pb, and Bi (Rajamani and Naldrett, 1978; Li and Agee,
2001; Gaetani and Grove, 1997; Wood et al., 2008; Mengason et al.,
2011). Most of these studies were performed with dry silicate melts
at 1 atm, and virtually all involved only sulde liquid, which is at
odds with the dominance of MSS in the source region and later
evolutionary stages of arc magmas (see below). An exception is a few
studies concerning the partitioning of Au, Ag, and Cu between
pyrrhotite and felsic silicate melt (Lynton et al., 1993; Jugo et al.,
1999; Simon et al., 2008). Thus, there is a great need for sulde
silicate melt partition coefcients at conditions relevant to the upper
mantle.
In this contribution we report a coherent set of partition
coefcients of V, M, Co, Ni, Cu, Zn, Mo, As, Sn, Sb, Ag, Au, W, Pb,
and Bi between coexisting MSS, sulde liquid, and hydrous
silicate melts representative of partial melts generated in metasomatized upper mantle. To exemplify the large number of
potential applications we use our results to model the inuence
of suldes on the behavior of Cu, Ag, and Au during melt
production in the upper mantle, and during fractional crystallization of primitive mantle melts in the lower crust.

 0.15
1.35
1.69
n.a.
n.a.
n.a.
n.a.
1.27
n.a.
n.a.
1.16
n.a.
n.a.
 1.18
1.89
1.30
 2.36
2.02
1.98

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

Fe3 /Fe

328

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

2.2. Sample capsules and control of fO2

Several capsule congurations were used to impose different
oxygen fugacities on the samples (Table 1). In all setups the
starting materials were loaded into San Carlos olivine capsules
(wall thickness 1 mm) in order to restrict interactions of the
suldes with the noble metal capsules to a minimum. In some
runs (LY01,19-25,31-33) the olivine capsule was placed directly
into a Pt95Rh05 capsule and the oxygen fugacity was kept at
intermediate values by the composition of the starting materials.
In this setup fO2 was not buffered, but was measured after the run

by Mossbauer
spectroscopy (see below).
Reducing conditions were obtained in three different ways. In
one run (LY26) the olivine container was loaded into a graphite
capsule that itself was placed into a Pt95Rh05 capsule. In run LY30
a similar graphite capsule was placed into an iron capsule that
sealed mechanically under high pressure. Another four experiments (LY12, LY15, LY16, and LY17) were performed with a
modied double capsule setup similar to that described in Bali
et al. (2010). In this method, a small inner Pt95Rh05 capsule
containing the olivine capsule plus the starting mix was loaded
into outer capsules made of Ni or Co, and the space between was
lled with corresponding oxides (NiO and CoO) and water. The
rst several experiments performed with a duration of 20 h all
failed because the sulde reacted to a volatile phase producing a
large cavity in the sample. Raman spectroscopic analysis of uid
inclusions trapped in the olivine capsule shows that the principal
components of the uid phase are H2S and H2O. This suggests that
hydrogen diffusing into the inner capsule continuously reacted
with the sulde and silicate to form H2S and H2O. After a few tries
it was clear that the run duration had to be reduced to about 2 h
in order for signicant amounts of hydrogen to diffuse in and the
sulde not getting exhausted.
To obtain relatively high oxidation states a conventional
double capsule setup (Chou, 1987) was used. The olivine containers were welded into small inner Pt95Rh05 capsules, which were
loaded together with buffer materials plus H2O into larger
Pt95Rh05 capsules (LY04, 08, 28, 29). Because the silicate melts
in these experiments are uid-undersaturated the oxygen fugacity attained in the sample is considerably lower than that in the
external buffer (see below). Thus, only strongly oxidizing buffers
(ReReO, Mn3O4Mn2O3) were used. In one run (LY30) a high
oxygen fugacity was achieved by adding B5 wt% anhydrite to the
starting mixture and welding the olivine capsule directly into a
Pt95Rh05 capsule.
2.3. High temperature and pressure equipment
All experiments were conducted at 1.53.0 GPa and 1175
1300 1C in end-loaded, solid media piston cylinder apparatus
using 0.5 in. diameter MgONaCl assemblies with stepped graphite heaters. The hot piston-in method was used to pressurize
the assembly. Temperature was monitored by PtPt90Rh10
(S-type) thermocouples with an estimated temperature uncertainty of 710 1C. A friction correction of 5% was applied to the
nominal pressure based a bracketing of the quartzcoesite transition at 790 1C and using the data of Bose and Ganguly (1995) as
reference. The experiments were quenched by switching off the
electrical power.
2.4. Analytical methods
2.4.1. Electron microprobe
Major elements in sulde liquid, MSS, and quenchable silicate
melts were measured with a JEOL JXA  8200 microprobe. The
analyses were performed in wavelengthdispersive mode, and a

329

PAP matrix correction was applied to the raw data. Suldes

were analyzed with 20 kV acceleration voltage and 20 nA beam
current, whereas quenched silicate melts were analyzed with
15 kV/10 nA. A defocused beam of 30 mm diameter was used for
all the standardizations and sample measurements. Both natural
and synthetic standards were used to calibrate the instrument.
For sulde analysis, Fe and S were calibrated on a synthetic
pyrrhotite with well-known Fe:S ratio, Ni, Co, and Cu were
calibrated on pure metals, and O was calibrated on magnetite.
For silicate melts, Na was calibrated on albite, Ca on wollastonite,
K on orthoclase, Ti and Mn on ilmenite, Si on enstatite, Mg on
forsterite, Al on spinel, P on GaP, Fe on metallic Fe, and Cl on
vanadinite. Sulfur concentrations in reduced and oxidized glasses
were calibrated on pyrrhotite and barite, respectively.
For sulde liquids, which unmixed into several phases at the
scale of  10 mm during quenching (Fig. 1(f), the use of a 30 mm
defocused electron beam resulted in well reproducible results.
In contrast, hydrous silicate melts displaying a coarse quench
texture (LY12, LY15, LY16, LY17) could not be analyzed reliably by
electron microprobe. In these samples, the major element composition was measured by LA-ICP-MS data and the results
normalized to 100 wt% major element oxides.
2.4.2. LA-ICP-MS
Major and trace elements of sulde liquid, MSS, nonquenchable silicate melt, and silicate minerals were analyzed by
LA-ICP-MS, using a Geolas M 193 nm ArF Excimer laser (Coherent/
Lambda Physik) attached to an Elan DRC-e quadrupole mass
spectrometer (Perkin Elmer Instruments). The laser was operated
at a frequency of 10 Hz and energy of 80 mJ for silicates; at a
frequency of 7 Hz and energy of 70 mJ for suldes. The laser beam
size ranged from 10 mm to 80 mm and was chosen as large as
possible to get an average composition of heterogeneously
quenched sulde liquid and silicate melt, and to obtain low
detection limits. The sample chamber was ushed with He at a
rate of 0.4 L/min, to which 5 ml/min H2 was added on the way to
the ICP-MS. Dwell times were 10 ms for the isotopes 23Na, 25Mg,
27
Al, 29Si, 39K, 42Ca, 49Ti, 51V, 55Mn, 57Fe, 59Co, 62Ni, 65Cu, 75As
93
Nb, 98Mo, 107Ag, 121Sb, 184W, 208Pb, and 209Bi, and 20 ms for
197
Au. NIST SRM 610 glass was used as external standard for all
analyses, whereas Al and Fe determined by electron microprobe
were used as internal standard for silicates and suldes, respectively. Tests on a synthetic monosulde solid solution standard
kindly provided by Lesley Rose and Jim Brenan (MSS-5) revealed
good agreement between LA-ICP-MS measurements and solution
ICP-MS data ( r10% deviations for Ni, Cu, Sb, and Pb; r15% for
Au and Bi, and 20% for Ag). A similar test on the PGE- and Aubearing Laamme Po724-T3 pyrrhotite standard (Sylvester et al.,
2005) returned an agreement between measured and certied
concentration within 3%. The uncertainties arising from internal
and external standardization are thus considered better than
1520% for all elements signicantly above the detection limit.
2.4.3. M
ossbauer spectroscopy
Samples containing relatively large volumes of quenched

silicate melt were measured using 57Fe Mossbauer

spectroscopy
to determine Fe3 /SFe in the silicate melt. The samples were
prepared as doubly polished thin sections with an effective
thickness of about 500 mm. Lead foils featuring holes of 200 or
400 mm in diameter were used to restrict the irradiation to areas
of pure silicate melt. Spectra were collected at room temperature

in transmission mode on a constant acceleration Mossbauer

spectrometer with a 50 mCi 57Co source in a 6 mm Rh matrix.
The velocity scale was calibrated relative to a 25 mm thick a-Fe
foil at room temperature. Mirror image spectra were recorded

330

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

Fig. 1. Petrography of experimental run products. (a) BSE image of sample LY28 (1200 1C, 1.5 GPa) showing partially melted silicate starting material and sulde phases
(bright globules) contained in an olivine capsule (dark gray). Silicate melt (light gray) accumulated at the top of the charge, which is located on the left. (b) BSE image of the
upper portion of sample LY26 (1200 1C, 1.5 GPa) showing pure silicate melt at the top and suldes plus crystals of olivine (dark gray) intermixed with silicate melt further
below. (c) Reected light image of the bottom part of hydrous sample LY16 (1200 1C, 1.5 GPa), which shows one exposed sulde globule (bright) and several epoxy-lled
vapor bubbles (dark globules at the rim of the charge) in non-quenchable silicate melt. (d) Transmitted light image of aqueous uid inclusions in the olivine liner of sample
LY15 (1200 1C, 1.5 GPa). (e) Reected light image of coexisting MSS, sulde liquid and silicate melt in sample LY04 (1185 1C, 1.5 GPa). The non-quenchable sulde liquid
forms a thin mensicus on top of MSS. (f) Reected light image of a large globule of sulde liquid at the bottom of sample LY12 (1300 1C, 1.5 GPa). The exsolution features in
the interior of the globule are characteristic of sulde liquid.

over 512 channels with a velocity range of 75 mm/s. Each

spectrum took at least 2 days to collect and was tted to Lorentzian

line shapes using the Recoil software package. The tted Mossbauer
spectra showed two strong absorbance doublets corresponding to
Fe2 and another shoulder corresponding to the absorption of Fe3 .
The Fe3 /SFe ratios were derived from the calculation of area
fraction of Fe3 in the total Fe area. Details regarding this technique
can be found in McCammon (2004).

3. Results
3.1. Sample petrography
The experimental conditions and obtained run products are listed
in Table 1, and representative textures are shown in Fig. 1. In runs
performed below 1200 1C, B510% silicate melt was produced at the
top of the charge (Fig. 1a, b). The rest recrystallized mainly to
amphibole, clinopyroxene, and olivine. In runs performed at
Z1200 1C, B1050% silicate melt was produced and the rest

recrystallized to clinopyroxene and olivine. The starting rock powder

contains B2 wt% H2O stored in amphibole (F and Cl contents are
 et al., 2001), thus decomposition of amphibole
very low; Fabries
during the run released signicant amounts of H2O into the silicate
melt. Based on the difference of EMPA totals to 100 wt% the water
content of the silicate melt produced in runs without H2O-containing
double capsules is estimated at B5 wt%.
The four reduced experiments performed in H2O-bearing double
capsules (LY12, LY15, LY16, and LY17) show a different texture.
Because the incoming hydrogen reacted with silicates to produce
H2O, the silicate melt became very water rich and saturated in an
aqueous H2OH2S uid, as demonstrated by numerous cavities in the
recovered samples (Fig. 1c) and the presence of uid inclusions in the
surrounding olivine capsules (Fig. 1d). Due to the high water content
the entire starting rock powder plus variable amounts of the
surrounding olivine capsule were melted in these runs, and the
silicate melts were not quenchable (Fig. 1c). Experimental data on
H2O solubility in the system Mg2SiO4SiO2H2O at 1.5 GPa
(Nakamura and Kushiro, 1974) suggest that these melts contained
Z20 wt% dissolved H2O.

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

331

Table 2
Partition coefcients (DMSS/SM) between MSS and silicate melt.
Exp. ID

Mn

Co

Ni

Cu

Zn

As

LY01
1s
LY04
1s
LY08
1s
LY15
1s
LY17
1s
LY19
1s
LY20
1s
LY22
1s
LY23
1s
LY24
1s
LY25
1s
LY26
1s
LY28
1s
LY29
1s
LY30
1s
LY31
1s
LY32
1s

n.d

0.24
0.02
0.19
0.01
0.14
0.01
0.19
0.00
0.17
0.00
0.22
0.01
0.21
0.01
0.21
0.03
0.20
0.01
0.20
0.02
0.22
0.09
0.18
0.03
0.16
0.01
0.14
0.01
0.17
0.02
0.10
0.00
0.10
0.00

69
5
46
2
46
3
33
2
25
3
40
3
57
3
41
2
37
1
39
1
33
2
47
2
39
3
41
1
45
7
30
1
33
3

790
150
510
80
270
50
260
50
230
90
580
100
1240
200
510
40
530
70
490
50
340
60
830
170
370
40
400
40
700
170
340
50
320
20

450
50
340
30
370
40
200
40
230
190
350
30
410
140
340
30
330
60
250
20
270
30
420
110
280
20
300
20
260
70
250
40
180
20

0.55
0.07
0.42
0.08
0.39
0.10
0.33
0.03
0.19
0.03
0.27
0.05
0.30
0.06
0.24
0.05
0.24
0.02
0.19
0.02
o 0.5

0.50
o 0.5
0.07
0.00
o 0.5

0.02
0.00
0.03
0.00
0.02
0.00
0.02
0.00
0.03
0.01
0.02
0.00
0.03
0.01
0.02
0.01
0.03
0.01
0.06
0.04
0.13
0.00
0.02
0.00
0.02
0.00
0.08
0.02
0.01
0.00
0.05
0.03

0.30
0.11
0.29
0.00
0.19
0.05
0.31
0.05
0.21
0.01
0.21
0.01

0.31
0.01
0.15
0.03
o 0.05
o 0.04
o 0.04
o 0.12
o 0.5
0.17
0.01
1.09
0.11
o 0.02
0.01
0.00
1.79
0.14
o 0.1
o 0.12

Mo

Ag

Sn

Sb

Au

Pb

Bi

1.78
0.30
0.42
0.03
0.60
0.10
0.42
0.02
0.20
0.01
0.62
0.07
0.35
0.02
0.42
0.05
0.62
0.04
0.79
0.02
0.68
0.06
14.48
0.75
0.29
0.01
0.64
0.05
9.99
1.26
0.21
0.01
0.95
0.14

42
6
31
3
68
22
23
6
25
15
64
12
34
7
76
18
69
6
28
7
28
4
67
19
29
3
28
2
110
60
22
8
19
3

0.09
0.01
0.10
0.02
o0.05

0.06
0.00
0.02
0.00
o 0.06

o 0.01

0.12
0.00
0.07
0.01
0.09
0.00
0.04
0.10
0.07
0.01
o0.1

0.02
0.00
0.08
0.02
0.03
0.01
0.01
0.00
0.02
0.00
0.02
0.00
0.02
0.00
0.23
0.02
0.13
0.01
0.01
0.00
o 0.04

0.00
0.00
0.06
0.01
0.01
0.01
0.07
0.06
0.31
0.18
o 0.02

160
40
60
10
90
40
n.d.

o 0.01

o0.4

0.14
0.04
o 0.2

o0.24

o 0.02

0.10
0.02
0.11
0.01
0.12
0.02
0.07
0.01
0.12
0.04
0.09
0.02
0.07
0.01
0.09
0.02
0.09
0.01
0.05
0.02
0.13
0.05
0.24
0.01
0.10
0.00
0.10
0.02
0.18
0.07
0.10
0.01
0.06
0.01

1.6
0.3
0.8
0.1
2.2
1.3
0.7
0.1
0.9
0.4
1.1
0.2
0.5
0.1
1.4
0.5
1.5
0.2
0.8
0.1
0.9
0.2
4.7
1.3
0.6
0.1
0.8
0.1
8.4
1.9
1.1
0.2
0.6
0.1

o0.1
o0.6
o1
o0.2
o1
o0.3

0.20
0.06
o 0.01

0.01
0.00
0.14
0.01
o 0.03
0.01
0.00
o 0.02

0.01
0.00
o 0.01

n.d.
310
30
140
20
140
80
210
20
190
40
200
60
200
70
170
120
360
130
140
60
220
20
190
100

n.d.not determined.

The PT conditions of most runs were chosen such that two

different sulde phases were present. One is crystalline MSS and
the other is sulde liquid (Fig. 1e), both being present as
individual, spherical globules within the charge. MSS quenches
to a homogeneous solid as evidenced by its optical appearance
and chemical homogeneity (Fig. 1e), whereas sulde liquid is not
quenchable and exsolves into an assemblage consisting of FeNirich MSS and Cu-rich sulde (chalcopyrite) (Fig. 1e, f). Where MSS
and sulde liquid are in direct contact with each other, the sulde
liquid is always pointing upward (Fig. 1e). At a constant pressure
of 1.5 GPa the phase proportions change from MSS only at 1175
1185 1C, over MSS sulde liquid at 11851200 1C, to sulde
liquid only at 1300 1C in good agreement with the phase diagram
of Bockrath et al. (2004a; cf. Fig. 4). The slightly higher solidus
temperature in our study can be explained by the lower Ni
content of our starting material (78 wt% versus 16 wt% in
Bockrath et al., 2004a). In runs LY12, LY15, LY16, and LY17, the
suldes agglomerated to a single sphere and sank to the bottom
of the olivine capsule. In these runs the extremely hydrous silicate
melt and coexisting uid phase may have taken up major
amounts of sulfur, which may have led to a change in the
metal/sulfur ratio of the residual sulde. For this reason these
runs are not considered in Fig. 4. Generally, only suldes and
silicate melts in direct contact with each other were selected for
analysis. Cases in which the phases were separated by minerals
were discarded, e.g., the MSS data in sample LY33.
3.2. Major and trace element content of silicate melt
The major and trace element contents of the silicate melts are
listed in supplementary Tables 2 and 3. From each sample 15 and

25 microprobe analyses were performed across the whole area of

silicate melt. In each of the four samples with non-quenchable
silicate melt ve 80 mm-sized Laser-ablation ICP-MS spots were
collected. Major elements are generally reproducible within 5%
and trace elements within 10%. All silicate melts are alkaline and
basanitic, consistent with the experimental results of Pilet et al.
(2008). The silicate melts of runs LY12, LY15, LY16, and LY17
contain considerably more Mg and less Al, Na, and K than the
other runs, which is due to the partial dissolution of the olivine
capsule in these experiments.
All measured trace elements were well above the detection
limit of our LA-ICP-MS and were homogeneously distributed in
the silicate melt, except for run LY17 which shows a relatively
larger range in Cu and Ag concentrations. Dissolved sulfur concentrations measured by EMPA increase from B0.15 to B1.4 wt%
as the oxygen fugacity increases from 3.1 log units below the
fayalitequartzmagnetite buffer to 1.0 log units above it (FMQ3.1 to FMQ 1.0). The full data set of sulfur analyses will be
reported along with Au concentrations and Au partition coefcients in a separate paper.
3.3. Major and trace element content of sulde phases
Major and trace element contents in MSS and sulde liquid are
listed in supplementary Tables 46. Major element abundances in
MSS and sulde liquids are well reproducible both among different
spots analyzed within one globule and among different globules
analyzed from the same sample. Compared to sulde liquid, MSS is
enriched in Fe and S, while sulde liquid has higher contents of Cu, Ni,
and O. The time-resolved LA-ICP-MS signals demonstrate that both
major and trace elements are homogeneously distributed in MSS.

332

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

Although this is obviously not the case in the unquenchable

sulde liquid, the size of the laser pits and the durations of
analyses were usually such that by integrating the signals representative averages could be obtained. In the sulde liquid analyzed from run LY16 tungsten is concentrated in phases that do
not seem to be quench products, as tungsten concentrations in
many other sulde liquids are below detection limit. These data
were thus rejected. Sn, Sb, and As were below detection limit in
MSS grown at relatively oxidizing conditions.

reported by Lagos et al. (2008) and Wood et al. (2008), but are
slightly higher than those reported by Shimazaki and MacLean
(1976) from the experiments performed in strongly simplied
SL=MSS
systems without control on fO2. DPb
is calculated from 130 to
430, which is comparable with a value of 200 reported by Jones
et al. (1993) from troilitesulde liquid partitioning at very reducing conditions. Thus, the presence of MSS has only little inuence
on the Pb content of coexisting silicate melt, whereas sulde liquid
has a considerable effect if present in signicant quantity.

3.4. Partition coefcients

3.4.2. Cu, Ag, and Au

SL=SM
MSS=SM
DCu and DCu
are relatively insensitive to oxygen fugacity,
changing by only about a factor of two over the investigated fO2
range. With increasing fO2 the partition coefcients rst increase,
SL=SM
and then decrease again. The maximum value of DCu
is located

Nernst partition coefcients (D) of major and trace elements

were calculated from their weights in sulde phases and silicate
melt. The data are tabulated in Tables 2 and 3, and are summarized and compared with literature values in Fig. 2. The effect of
oxygen fugacity on the partition coefcients of selected elements
is shown in Fig. 3. In the following sections SL refers to sulde
liquid, MSS refers to monosulde solid solution, and SM refers to
silicate melt. Literature data are commonly available for sulde
liquidsilicate melt partitioning (SL/SM) and sulde liquid
monosulde solid solution (SL/MSS) partitioning, but only rarely
for monosulde solutionsilicate melt (MSS/SM) partitioning.
3.4.1. Bi and Pb
The partition coefcient of bismuth between sulde liquid and
SL=SM
silicate melt, denoted as DBi
, ranges from 110 to 1130, whereas
MSS=SM
DBi
is about two orders of magnitude lower and ranges from
SL=SM
MSS=SM
0.6 to 8.4. Both DBi
and DBi
decrease with increasing oxygen
fugacity. The Bi content of a suldesaturated silicate melt thus
depends mainly on the type and amount of sulde present plus on
oxygen fugacity, given that silicate minerals do not accommodate
appreciable amounts of Bi (Adam and Green, 2006).
SL=SM
DPb
ranges from 14 to 48 and is about two orders of
MSS=SM
magnitude higher than DPb
, which ranges from 0.1 to 0.24.
Both partition coefcients decrease only slightly with increasing
SL=SM
oxygen fugacity. Our values of DPb
are within the range of values

MSS=SM

SL=SM

at BFMQ  1. The DCu

values
at BFMQ0.5, and that of DCu
of 9001100 obtained at FMQ 0.2 to FMQ0.7 agree well with
the values of 9131383 obtained from coexisting sulde liquid
and MORB (Peach et al., 1990; Francis, 1990) in which system the
oxygen fugacity is generally believed to be around FMQ. Our data
are also within the data range reported in Ripley et al. (2002) and
Gaetani and Grove (1997), but are approximately ve times
higher than the data of Rajamani and Naldrett (1978) and
Maclean and Shimazaki (1976) whose experiments were conMSS=SM
ducted at unknown oxygen and sulfur fugacity. DCu
ranges
from 180 to 450, which is comparable to the value of 329 835
obtained by Lynton et al. (1993) at oxidizing conditions, but about
one order of magnitude lower than the data of Jugo et al. (1999),
and slightly higher than the data of Simon et al. (2008). All of
SL=MSS
these studies were performed with felsic melts. Our DCu
values
range from 1.4 to 3, which are within the range of values reported
by Li et al. (1996) and Ballhaus et al. (2001).
SL=SM
DAg
remains constant at B1000 up to a fO2 of BFMQ 0.5,
MSS=SM
above which it slightly decreases. In contrast, DAg
decreases
regularly from B100 to B30 with increasing oxygen fugacity.
MSS=SM
The DAg
values agree well with those of Simon et al.
(2008) obtained in felsic melts at NiNiO, and the corresponding

Table 3
Partition coefcients (DSL/SM) between sulde liquid and silicate melt.
Exp. ID

Mn

Co

Ni

Cu

LY04
1s
LY08
1s
LY12
1s
LY16
1s
LY17
1s
LY25
1s
LY26
1s
LY28
1s
LY29
1s
LY30
1s
LY31
1s
LY32
1s
LY33

0.06
0.00
0.02
0.00
0.07
0.01
0.05
0.00
0.02
0.00
0.04
0.00
0.03
0.01
0.03
0.01
0.02
0.00
0.03
0.02
0.02
0.00
0.03
0.00
0.02

0.29
0.01
0.17
0.00
0.40
0.01
0.24
0.01
0.26
0.02
0.20
0.02
0.15
0.02
0.20
0.04
0.15
0.00
0.17
0.02
0.21
0.04
0.10
0.01
0.19

29
1
39
2
33
3
28
6
23
3
30
1
47
2
31
2
35
1
49
8
33
6
26
2
32

520
80
490
90
210
90
1010
140
250
100
440
60
1180
110
470
60
620
60
1270
260
470
110
450
20
450

1s

0.00

0.01

20

n.d.not determined.

Zn

As

Mo

Ag

Sn

Sb

1040
90
1070
70
540
140
600
160
330
280
800
90
720
40
820
40
910
50
600
120
740
150
540
40
540

0.94
0.10
o 0.5

0.7
0.0
o 0.5

0.15
0.01
o 0.2

5.9
0.3
3.6
0.1
6.0
0.7
4.7
0.8
3.2
1.0
6.4
1.8
6.3
0.6
3.1
0.7
3.3
0.1
8.6
0.3
2.7
0.4
2.2
0.2
2.4

3.5
0.1
2.2
0.1
3.8
1.1
9.3
3.4
1.4
0.6
5.2
1.7
8.5
0.7
2.0
0.3
2.1
0.2
11.2
0.5
1.6
0.2
1.6
0.3
2.8

0.003
0.00
o 0.01

0.67
0.13
5.15
0.34
0.13
0.01
0.15
0.02
5.10
1.28
0.10
0.02
0.73
0.03
3.46
1.02
0.14
0.07
0.26
0.12
2.58

1680
110
950
70
480
80
420
80
300
200
1050
150
920
160
890
70
970
40
970
100
610
230
450
100
470

0.98
0.13
0.77
0.15
0.47
0.10
0.60
0.05
0.39
0.08
0.54
0.26
0.40
0.02
0.55
0.10
0.58
0.08
0.28
0.01
0.50

1.0
0.2
19.7
5.4
0.3
0.1
1.9
0.7
10.5
1.0
0.3
0.1
0.3
0.0
15.4
0.8
0.3
0.1
0.6
0.1
1.1

60

0.04

0.1

0.91

130

0.2

0.4

0.01
0.00
n.d
0.43
0.19
o 0.0
o 0.1
o 0.01
0.06
0.00
o 0.01
o 0.01
o 0.01
o 0.1

Au

Pb

Bi

4470
560
790
310
n.d.

48
2
28
1
32
7
10
5
24
11
45
13
31
5
27
4
27
2
45
1
23
3
14
2
24

350
10
210
20
140
80
850
120
130
70
420
110
800
140
170
40
200
20
1130
60
130
30
110
20
120

10

n.d.
n.d.
930
270
2720
70
3690
1630
4070
1390
2360
560
5500
740
2650
740
2380
350

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

(1990), Gaetani and Grove (1997), Rajamani and Naldrett (1978),

and Francis (1990), but are several times lower than the data of
Peach and Mathez (1993). The disagreement with the latter data
seems to be due to differences in oxygen fugacity, sulfur fugacity,

10000
1000

MSS=SM

DSL/SM

100
10
1
0.1
0.01
0.001
V Mn Co Ni Cu Zn As Mo Ag Sn Sb W Au Pb Bi

and the composition of the sulde liquid. DNi

shows a similar
SL=SM
behavior as DNi , decreasing from B800 to B300 as fO2 increases.
SL=MSS
Corresponding DNi
values range from 1.0 to 1.8, which are
within the range of values reported by Fleet et al. (1993, 1996),
Li et al. (1996), and Ballhaus et al. (2001).
SL=SM
MSS=SM
DCo
and DCo
depend only weakly on oxygen fugacity and
vary from 30 to 50 and 30 to 60, respectively. These values are
consistent with the sulde liquid-MORB partitioning data of
Peach et al. (1990) and are within the range reported by
SL=SM
MSS=SM
Gaetani and Grove (1997). The similarity of DCo
and DCo
suggests that the behavior of Co in sulde-bearing silicate melts
does not depend on the type of sulde present.
3.4.4. V, Mn, W, and Zn
These four elements are incompatible in both MSS and sulde
liquid, with DSL=SM and DMSS=SM values below unity. The Zn
partitioning data of MacLean and Shimazaki (1976) and
Shimazaki and Maclean (1976) are consistent with this observaSL=SM
tion. Higher DZn
values reported by Logas et al. (2008) and
SL=SM
Wood et al. (2008) 1 o DZn o10 may be due to the extremely
low fO2 of these experiments. Our V, Mn, and W partition
coefcients are consistent with the data of Gaetani and
Grove (1997) and are within the range found by Lodders
and Palme (1991). Some higher values in the latter study
SL=SM
0:03 o DW
o3:1 seem to be related to very low oxygen
SL=SM
fugacities. A DW
value of 9 was reported by Mengason et al.
(2011) in a study with felsic melt. These results suggest that
suldes are a negligible carrier of V, Mn, W, and Zn in magmas.

1000
100
10

DMSS/SM

333

1
0.1
0.01
0.001
V Mn Co Ni Cu Zn As Mo Ag Sn Sb W Au Pb Bi
SL/SM

Fig. 2. Sulde liquidsilicate melt partition coefcients (D

) and monosulde
solid solutionsilicate melt partition coefcients (DMSS/SM) determined in this
study (colored symbols) compared to the literature data (light crosses; entire
range covered by gray bars). For references regarding the literature data, see the
text. Yellow triangles refer to data obtained at oxygen fugacities between FMQ  3
and FMQ  1; red circles refer to data obtained at oxygen fugacities between
FMQ  1 and FMQ 0.5; blue diamonds refer to data obtained at oxygen fugacities
between FMQ 0.5 and FMQ 1. (For interpretation of the references to color in
this gure caption, the reader is referred to the web version of this article.)
SL=MSS

DAg
values are consistent with the experiment data of Jones et al.
(1993), but are one order of magnitude higher than the value
estimated by Barnes et al. (2006) on magmatic sulde ore deposits.
SL=SM
MSS=SM
DAu
and DAu
values will be discussed in detail in a
complementary paper (Li and Audetat, in preparation). Both
SL=SM
MSS=SM
DAu
and DAu
do not show much dependence of oxygen
MSS=SM
SL=SM
fugacity, with DAu
180 780 and DAu 3400 71200.
In summary, the compatibility of these three elements in
sulde liquid decreases in the order Au4CuE Ag, and their
MSS=SM
compatibility in MSS in the order Cu4Au4 4 Ag. DAu
is
SL=SM
B20 times lower than DAu
at all conditions. Thus, a silicate
melt equilibrated with MSS contains more Cu, Au, and Ag than the
same melt equilibrated with an equivalent amount of sulde
liquid. Continuous exsolution of sulde liquid from a crystallizing
magma results in approximately constant Cu/Ag ratios but
decreasing Au/Ag and Au/Cu ratios in the silicate melt, whereas
continuous exsolution of MSS causes all three ratios to decrease.

3.4.3. Ni and Co
SL=SM
DNi
decreases from 1300 to 200 as the oxygen fugacity
increases. Our values are comparable to those of Peach et al.

3.4.5. Sn, Sb, As, and Mo

DSL=SM and DMSS=SM values of these four elements are rather
sensitive to variations in fO2. The maximum values are obtained
at reducing conditions, but they do not exceed 15 and 5,
respectively. Sn, Sb, and As prefer sulde liquid over MSS, which
is consistent with the ndings of Helmy et al. (2010). In contrast,
SL=SM
Mo prefers MSS over sulde liquid. The much higher DMo values
of 60200 reported by Lodders and Palme (1991) might be due to
low oxygen fugacities in these experiments. The recent study on
SL=SM
pyrrhotitesulde liquidrhyolite system gave a DMo value of 30
and showed that Mo preferentially partitions into sulde liquid
rather than MSS at oxygen fugacity of NiNiO buffer (Mengason
et al., 2011). Our results suggest that limited amounts of suldes
in natural magmas do not affect the abundance of these elements
in the silicate melt.

4. Discussion
4.1. Estimation of oxidation state and sulfur fugacity
The basic principle of external oxygen buffering involves
diffusion of hydrogen through a permeable membrane
(Pt95Rh05 in our case) and dissociation equilibria of H2O on
both sides of the membrane (Chou, 1987). To obtain equal
oxygen fugacities in the sample and the external buffer the
activities of water in the two reservoirs need to be the same. In
this study the silicate melts produced in oxidized runs were
signicantly water-undersaturated, for which reason the oxidation states in these samples are expected to be signicantly
lower than the ones in the external, H2O-saturated ReReO and
MnOMn3O4 buffers (Luth, 1989).

334

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

Ag

1000

As

10
1

100
0.1
10

DSL/SM
MSS/SM
D

-3

-2

1000

0.01
-1

Bi

100

-3

-2

60

10

40

Co

80

100

-1

1
20

0.1
-3

-2

-1

-3

-2

Mo

Cu

1000

-1

10

0.1
100
-3

-2

-1

1500

100

-3

-2

-1
Pb

Ni
1000

10
1

500

0.1
0.01
-3

-2

-1

-3

-2

Sn

Sb

10

-1

10

1
0.1
0.01
1
-3

-2

-1
FMQ

-3

-2

-1
FMQ

Fig. 3. DMSS/SM (black dots) and DSL/SM (open diamonds) partition coefcients as a function of log fO2 relative to FMQ. Only data from runs with fO2 conditions determined
after the experiment by either Fe3 / SFe (LY01, 04, 08, 19, 23, 26, 28, 29, 31, 32) or Dolivine/melt
(LY30) are plotted in this gure. For simplicity, the error bars regarding fO2
V
are shown only in the rst plot.

Although the partial melts produced in runs externally buffered by NiNiO, CoCoO, and FeOFe3O4 were initially
water-undersaturated too, diffusion of hydrogen into the capsules

and its interaction with silicate melt resulted in the production of

H2O and ultimately in saturation with an aqueous uid phase.
Thus, these samples ultimately reached approximately the same

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

oxygen fugacities as those imposed by the external buffers.

A close correspondence between external and internal fO2 is
conrmed by the partitioning behavior of redox-sensitive elements such as Mo. For example, hydrous run LY16 buffered at Co
CoO returned a sulde liquidsilicate melt partition coefcient of
5.2, which is close to the value of 5.1 measured in less hydrous
run LY26 equilibrated at a similar oxygen fugacity, and hydrous
run LY17 buffered at NiNiO returned a sulde liquidsilicate
melt partition coefcient of 0.13, which is close to the value of
0.15 observed in less hydrous run LY08 equilibrated at a similar
oxygen fugacity.
In those experiments in which fO2 was either not buffered at
all or was expected to be signicantly lower than the fO2 imposed
by external buffers the oxidation state of the sample was
estimated based on the Fe3 /SFe ratio in the silicate melt using
the calibrations of Jayasuriya et al. (2004) and ONeill et al. (2006).
In sample LY30, in which the melt pool was too small to be

analyzed by Mossbauer
spectroscopy, fO2 was estimated based on
olivine-melt partitioning of vanadium using the calibration of
Canil (1997). A test on sample LY26 shows a good agreement
between fO2 estimated based on Fe3 /SFe (FMQ-2.6) and that
based on vanadium partitioning (FMQ-2.1).
Sulfur fugacities can be estimated from the composition of the
silicate melt in equilibrium with MSS based on the reaction
2FeOsilicate melt S2 2FeSMSS O2, (Bockrath et al., 2004b). To be
able to extend the 1 atm calibration of Bockrath et al. (2004b) to
high pressures, a volume change term was added by Liu et al.
(2007). Sulfur fugacities in our samples were thus estimated
based on equation (2) in Liu et al. (2007). The presence of
23 wt% Cu and 78 wt% Ni in our MSS has a negligible effect
on calculated fS2 (Kosyakov et al., 2003; Raghavan, 2004;
Mengason et al., 2010).
4.2. Attainment of equilibrium
The time required for chalcophile elements to attain equilibrium between sulde and silicate melt at temperatures above
1000 1C has been shown to be short. Maclean and Shimazaki
(1976) reported that equilibrium partitioning of Ni, Co, Cu, and Zn
between dry silicate melts and suldes was attained after only
15 min at 1150 1C. Rajamani and Naldrett (1978) demonstrated
by forward and reverse runs that equilibrium partitioning of Fe,
Co, Ni, and Cu in similar experiments was reached in less than
12 h at 1255 1C. Several lines of evidence suggest that equilibrium was also reached in our experiments. First, both the silicate
melt and sulde phases are compositionally homogeneous with
respect to both major and trace elements. Second, the partition
coefcients do not show any dependence on run duration or the
element concentrations in the starting sulde, but vary as a
function of oxygen fugacity (see below). Third, our data compare
well with the literature data, particularly if looking at the studies
using natural silicate melts such as MORB (Peach et al., 1990;
Francis, 1990).
4.3. Summary and signicance of the partitioning data
In summary, the partition coefcients of most elements
investigated in this study are affected mainly by oxygen fugacity
and/or the type of sulde present. Variations in temperature and
pressure have no signicant effect in the range from 1175 1C/
1.5 GPa to 1300 1C/ 3 GPa, the same as variations in the water
content (from B5 wt% to 410 wt% H2O) and (MgO FeO)/
(Al2O3 Na2OK2O) ratio (0.92.2), of the silicate melt. A comparatively small dependence on melt composition is also indicated by the good agreement of the present data with those
determined on natural sulde melt globules in MORB glasses

335

(Francis, 1990; Peach et al., 1990), which melts contain much less
water ( o0.5 wt% H2O) and alkalies than those of the present
study. This means that the partition coefcients determined in
the present study should be applicable to mantle melting and
magma crystallization in a large range of tectonic settings,
including MORB and arc environments. SL/SM partition coefcients decrease in the order Au4Ni, Cu, Ag, Bi 4Co, Pb4Sn, Sb,
As, with the remaining elements fractionating into the silicate
melt. MSS/SM partition coefcients decrease in the order Ni, Cu,
Au4Co, Ag4Bi, Mo, with the remaining elements fractionating
into the silicate melt. SL/MSS partition coefcients are almost
always 41 and decrease in the order Pb4Bi, Sb4Au4Ag4Cu,
As4Mo, Ni4remaining elements. Most suldesilicate melt
partition coefcients vary as a function of fO2, with Mo, Bi, As
( 7W) varying by a factor 410 over the investigated fO2 range,
Sb, Ag, Sn ( 7V) varying by a factor of 310, and Pb, Cu, Ni, Co, Au,
Zn, Mn varying by a factor of o3. To constrain the abundance of
suldes in magmatic environments elements with very high
SL/SM partition coefcients (e.g., Au, Cu, Ag, and Bi) are most
appropriate. To constrain the type of sulde present elements
with high SL/MSS partition coefcients (e.g., Pb, Bi, Sb, and Ag) are
most appropriate. Thus, combinations between Au, Cu, Ag, and Bi
are best suited to constrain both the absolute abundance and type
of sulde present. The capability of this approach is illustrated by
the following two applications.

5. Applications
5.1. Constraints on the metal content of primitive mantle melts
During partial melting, the concentration of metals in the
silicate melt depends on the abundances of MSS and sulde liquid
in the mantle source, the corresponding partition coefcients, and
the degree of partial melting. The experimental study of Bockrath
et al. (2004a) showed that in the upper mantle both MSS and
sulde liquid may coexist, which result is conrmed by the
present study. According to the sulde phase diagram of
Bockrath et al. (2004a) and estimated PT conditions of magma
production in MORB and arc settings (Fig. 4), suldes in the
source region of MORB are probably dominated by sulde liquid,
whereas in the source region of arc magmas they are probably
dominated by MSS.
The abundance of sulfur in the source region is a critical factor
with regard to the behavior of metals during partial melting.
Studies on mantle peridotite xenoliths have shown that sulfur is
heterogeneously distributed in the upper mantle (e.g., Lorand,
1990; McInnes et al., 2001; Lee, 2002; Alard et al., 2011). For the
depleted mantle source of MORB an average sulfur concentration
of 190750 mg/g was estimated by several authors (Lorand, 1990;
Saal et al., 2002; Bezos et al., 2005), whereas for primitive mantle
a concentration of 250750 mg/g was estimated by McDonough
and Sun (1995). Metasomatized mantle seems to be enriched in
sulfur. Average concentrations of 250500 mg/g were estimated
for metasomatized arc mantle by Metrich et al. (1999) and
de Hoog et al. (2001), while individual mantle xenoliths contain
up to 1190 ppm sulfur (McInnes et al., 2001). A positive correlation between the degree of hydrous metasomatism, sulfur enrichment and increased oxidation state has been noted in many cases
(e.g., McInnes et al., 2001; Rowe et al., 2009; Wallace and
Edmonds, 2011).
In the following model, absolute and relative concentrations of
the highly chalcophile elements Cu, Au, and Ag in primitive arc
basalt were modeled as a function of degree of partial melting and
the relative abundances of MSS versus sulde liquid in the mantle
source (Fig. 5). The latter was assumed to have an oxidation state

336

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

of FMQ 1 (Parkinson and Arculus, 1999; Frost and McCammon,

2008), a sulfur content of 350 mg/g, and the Cu, Au, and Ag
concentrations estimated for depleted mantle (Salters and
Stracke, 2004). Using these numbers, the average Cu content of
suldes turns out at 3.0 wt% (assuming that no Cu is stored
in other phases), which agrees well with the Cu content of
natural mantle suldes. The following partition coefcients were
MSS=SM

used: DCu

MSS=SM

280, DAg

MSS=SM

SL=SM

40, DAu

180, DCu

180,

4
us

lid

so

ite

ot

d
lfi

rid

su

Pressure (GPa)

dr

Arc

sulfide

pe

us

lid

so

liquidu

2
%

0.

wt

O
H2
%

we

tp
e

5
0.0

r id

o ti

te

wt

sol

O
H2

MORB

id u

0
1100

1000

1200
1300
Temperature (C)

1400

1500

Fig. 4. PT diagram showing the phase relations of sulde according to Bockrath

et al. (2004a) and the effect of added volatiles on the mantle solidus. Gray symbols
represent data points of Bockrath et al. (2004a) (full squares MSS; half-lled
squares MSS coexisting with sulde liquid; open squares sulde liquid). Black
and white symbols represent data points of this study (full circle MSS; half-lled
circle MSS sulde liquid; open circle sulde liquid). Notice the generally good
agreement between the results obtained by Bockrath et al. (2004a) and those of
the present study. Dry peridotite solidus is from Katz et al. (2003), wet peridotite
solidus is from Grove et al. (2006), and solidi with 0.05 and 0.1 wt% H2O added are
from Katz et al. (2003). Estimated PT conditions of partial melting for arc
magmas and MORB are shown as blue and red elds, respectively. The former
are based on Sobolev and Chaussidon (1996), Ulmer (2001), Pichavant et al.
(2002), Johnson et al. (2009), and Kimura et al. (2009), and the latter are based on
Kushiro (2001) and Presnall and Gudnnsson (2008). (For interpretation of the
references to color in this gure caption, the reader is referred to the web version
of this article.)

SL=SM

DAg

3400. At a sulfur content of 350 mg/g

in the source and a sulfur solubility of 2500 mg/g S in the silicate

melt (Jugo et al., 2010), sulde exhaustion occurs at 14 wt%
partial melting. For melting in the presence of both MSS and
sulde liquid we assumed constant relative proportions of these
two phases until total sulde exhaustion. Whether or not sulde
melts can be extracted by physical means (i.e., as entrained
droplets) is still a matter of debate (e.g., Ballhaus et al., 2006;
Barnes et al., 2008). Experimental and theoretical studies on melt
extraction from partially molten mantle suggest that partial
melting is near-fractional (Kelemen et al., 1997; Kohlstedt and
Holtzmann, 2009). We thus modeled the process as fractional
melting in steps of 1 wt% melting. The effects of batch melting
would be qualitatively the same but less pronounced. Similarly,
changes in the sulfur content of the source and/or the sulfur
solubility in the partial melt result in trends that are qualitatively
the same, but sulde exhaustion is attained at different degrees of
partial melting (e.g., at 1000 mg/g instead of 350 mg/g S in the
source, sulde exhaustion is reached at 40 wt% instead of 14 wt%).
The modeling results show that the absolute abundances of Cu,
Au, and Ag in the silicate melt increase with increasing degree of
partial melting, except for Ag in the case of a high proportion of
MSS. The calculated element concentrations and element ratios
agree well with actual concentrations reported from primitive arc
magmas (Jenner et al., 2010). Ratios of Cu (which has a DSL=MSS of
1.43) to Ag and Au (which have DSL=MSS values of 1050 and  20,
respectively) are sensitive to the proportion of MSS relative to
sulde liquid (Fig. 5b). For example, at high MSS fractions the
Cu/Au ratio in partial melts increases with increasing degree of
partial melting, whereas at intermediate to low MSS fractions the
Cu/Au ratio in the melt decreases. Since MSS seems to be the
dominant sulde in the source region and during later evolution
of arc basalts (see below), the Cu/Au ratio in the silicate melt may
thus increase with increasing degree of partial melting. This result
is in contrast to previous models in which the Cu/Au ratio was
considered to decrease with increasing degree of partial melting,
leading to arc magmas with particularly high Au/Cu ratios when
sulde exhaustion is approached (Mungall, 2002; Richards, 2009).
These models are correct only if the dominant sulde phase in the
source region is sulde liquid.

106

1000
Cu MSS

Cu

Cu SL

10
1

Ag M

SS

0.1

Ag SL

Ag

0.01
Au MSS

Au

0.001

Cu/Au SL

105
metal ratio in silicate melt

100
conc. in silicate melt (ppm)

SL=SM

1000, and DAu

Cu/Au MSS

Ag

Cu/

1000

MS

Cu/Ag

100
Ag/Au SL
Ag

10

/Au

Au SL

0.0001

Cu/Au

Cu/Ag SL

104

Ag/Au
MS

1
0

10
15
% partial melting

20

10
15
% partial melting

20

Fig. 5. Modeled Cu, Au, Ag concentrations and Cu/Au, Cu/Ag, Ag/Au ratios in primitive arc basalt as a function of the degree of parial mantle melting and the proportion of
MSS relative to sulde liquid (0 wt% MSS, 50 wt% MSS, and 100 wt% MSS). The process was modeled as fractional melting with steps of 0.7 wt% melt production. Sulde
exhaustion occurs at 14 wt% melting. The gray boxes on the right show the ranges of natural, arc-like magmas reported by Jenner et al. (2010). Notice that the Cu/Au ratio
increases with increasing degree of partial melting if the proportion of MSS is very high.

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

1000

35
Ag MSS

100

Bi
Au MSS

10

Au

SS

Bi SL
Ag

SL

SL

0.1

conc. in silicate melt (ppb)

40

conc. in silicate melt (ppb)

10000

0.01

337

Ag
Bi
Au

30
25
20
15
10
5

0.001
0

20

40
60
% crystallization

80

0
10

100

7
6
MgO (wt%)

Fig. 6. (a) Modeled concentrations of Ag, Au, and Bi in sulde-saturated MORB as a function of the degree of fractional crystallization and proportion of MSS relative to
sulde liquid. (b) Measured concentrations of Ag, Au, and Bi in variously differentiated MORB according to Jenner et al. (2010). The increasing Bi concentration but
decreasing Ag concentration with decreasing amount of MgO in the silicate melt implies that MSS made up between 28% and 70 wt% of the precipitating sulde.

Cu

/A

SL

106

Cu/Au MS

104

Cu/Ag

100
80

SL

Cu

/A

SL

/A

100

Ag/Au

10

Cu/Au

60
1000

Ag

metal ratio in silicate melt

105

SS

40

20

MSS

1
0

20

40
60
% crystallization

80

10

100

6
4
MgO (wt%)

100

Ag/Au

10000

Cu/Ag

1000

10

100
10

6
4
MgO (wt%)

10

6
4
MgO (wt%)

Fig. 7. (a) Modeled Cu/Au, Cu/Ag, and Ag/Au ratios in arc basalt as a function of the degree of fractional crystallization and the proportion of MSS relative to sulde liquid.
The magma is assumed to be initially sulde undersaturated, reaching saturation at 40% crystallization. (b) Measured Cu/Au, Cu/Ag, and Ag/Au ratios in natural, arc-like
magmas as reported by Jenner et al. (2010). The observed trends require Z95 wt% MSS in the precipitating sulde.

338

Y. Li, A. Andreas / Earth and Planetary Science Letters 355-356 (2012) 327340

5.2. Constraints on the type of sulde phase(s) present during

magma differentiation
The solubility of sulfur in silicate melts is a function of temperature, pressure, melt composition, and oxygen fugacity. Decreasing
magma temperature, crystallization of Fe-bearing minerals, and
increasing SiO2 content all leads to a decrease in sulfur solubility.
Thus, basically any magma that has experienced signicant fractionation should be sulde-saturated (Parat et al., 2011). If sulde saturation is common in magmas, which type of sulde phase can be
expected for magmas of different tectonic settings? Arc magmas
crystallize at lower temperatures and higher pressures than MORB
and thus are more likely to precipitate MSS. This trend is supported
by the recent data on chalcophile element concentrations in variously
differentiated MORB and arc magmas (Jenner et al., 2010). Based on
constant Cu/Ag ratios but increasing Cu/Au ratios with increasing
degree of differentiation these authors concluded that MORB magmas
fractionated mainly sulde liquid, whereas arc fractionated dominantly MSS. The suldesilicate melt partition coefcients presented
in this study allow the conclusions of Jenner et al. (2010) to be tested
quantitatively.
Sulfur content and sulfur solubility in arc basalts were chosen to
be 0.15 wt% and 0.25 wt%, respectively, whereas for MORB both
values were set at 0.1 wt% (i.e., the arc basalts were assumed to be
initially sulde-undersaturated, and MORB were assumed to be
sulde-saturated from the beginning). The starting concentrations
of Cu, Ag, Bi, and Au in the silicate melt were 200, 0.05, 0.005, and
0.005 ppm in both cases. For MORB we used the following sulde
MSS=SM
MSS=SM
silicate melt partition coefcients: DBi
2, DAg
40,
MSS=SM

DAu

SL=SM

180, DBi

SL=SM

500, DAg

SL=SM

1100, and DAu

MSS=SM
DCu

3400,

MSS=SM

whereas for arc basalts we used

280, DAg
40,
MSS=SM
SL=SM
SL=SM
SL=SM
DAu
180, DCu 180, DAg
1000, and DAu
3400. Crystallization was assumed to be fractional (modeled in steps of 3 wt%),
and sulfur and metals were assumed to be 100% incompatible in all
minerals except for suldes. For the scenario that involves precipitation of both MSS and sulde liquid the relative proportions of these
two phases were assumed to remain constant during the entire
crystallization interval (which is of course an oversimplication).
The modeling results for MORB are shown in Fig. 6a. The strongly
decreasing Ag concentrations with decreasing MgO contents of
natural MORB (Fig. 6b) suggest that the proportion of SL in the
precipitating suldes was at least 50 wt%, whereas the slightly
increasing Bi concentrations require a similar amount of MSS being
present. Thus, although SL not necessarily had to be dominant, it
certainly made up a major fraction of the precipitating suldes. This
conclusion is consistent with the nding of Bezos et al. (2005) that
residual MSS is required to explain the PGE patterns observed
in MORB.
The modeling results for arc basalts are shown in Fig. 7a.
Measured metal ratios in the Pual Ridge magmas remain nearly
constant until the MgO content of the silicate melt becomes less than
4 wt% (Fig. 7bd), and then suddenly increase or decrease. This
suggests that originally sulde-undersaturated magmas reached
sulde saturation at B4 wt% MgO. The fact that Cu/Ag and Cu/Au
in the Pual Ridge magmas decrease with increasing differentiation
(Fig. 7b and c) requires a very high proportion (495%) of MSS in the
precipitating suldes, as already minor amounts of sulde liquid lead
to increasing Cu/Ag and Cu/Au with increasing differentiation
(Fig. 7a). Thus, the modeling results for both MORB and arc basalts
support the conclusions drawn by Jenner et al. (2010).
Acknowledgments
We like to thank Hans Keppler for discussions, Catherine

McCammon for discussions and help with the Mossbauer

analyses,

Sebastian Pilet for providing the AG4 starting material, Frances

Jenner for sharing her whole-rock analyses of MORB and arc
basalts, and Detlef Kraue and Julia Huber for help with the
microprobe analyses. Thoughtful comments by editor Tim Elliott
and an anonymous reviewer greatly helped to improve the paper.

Appendix A. Supporting information

Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.epsl.2012.08.008.

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