©2013 Society of Economic Geologists, Inc.

Economic Geology, v. 108, pp.1971–1982

Sulfide-Olivine Fe-Ni Exchange and the Origin of Anomalously Ni Rich

Magmatic Sulfides
Stephen J. Barnes,1,† Bélinda Godel,1 Derya Gürer,2,* James M. Brenan,3 Jesse Robertson,1 and David Paterson4
1 CSIRO Earth Science and Resource Engineering, 26 Dick Perry Ave., Kensington, Perth, WA 6151, Australia
2 Rheinische Friedrich-Wilhelms Universität Bonn, Steinmann Institut, Poppelsdorfer Schloss, 53115 Bonn, Germany
3 Department of Earth Sciences, University of Toronto, 22 Russell St., Toronto, Ontario M5S 3B1, Canada
4 Australian Synchrotron, 800 Blackburn Rd., Clayton, VIC 3168, Australia

Abstract
Equilibration between sulfide liquid and olivine is expressed in terms of the exchange coefficient for Fe and
Ni, KD = (XNiS/XFeS)sulfide_liquid / (XNiO/XFeO)olivine . The positive dependence of KD on Ni + Cu content of sulfide
liquid, as well as on fO2, has been demonstrated experimentally and gives rise to a critical nonlinearity in the
relationship between sulfide and olivine-saturated silicate liquid compositions. Measured KD values for olivine-
sulfide pairs from disseminated magmatic sulfide ores at Betheno (Western Australia) and Mirabela (Brazil) are
consistent with independent estimates of fO2, and fall within the range where the composition dependence of
KD is strong. This effect has been modeled quantitatively, using an empirical best fit to available experimental
data as a parameterization of the KD variability, and calculating the equilibrium distribution of Fe, Ni, and Mg
between coexisting olivine, silicate melt, and sulfide liquid as a function of the silicate/sulfide mass ratio R. It
is shown that the composition dependence of KD is a key factor in giving rise to extremely Ni rich sulfides as
exemplified by Betheno and Mirabela, where coexisting olivine is also Ni rich. Highly Ni enriched sulfides with
anomalously high Ni/Cu ratios may be more common in nature than is commonly recognized and do not need
to be explained by hydrothermal alteration processes.

Introduction fugacity. The positive dependence of KD (and hence D) on

One of the most fundamental research questions on the ori-
gin and composition of magmatic Ni-Cu sulfide deposits is
the nature of the thermodynamic control on Ni partitioning
between silicate melt, sulfide melt, and coexisting silicate min-
erals. Conventionally, partitioning of chalcophile elements has
been expressed and modeled in terms of simple Nernst parti-
tion coefficients (D) allowing for temperature and composi-
tion dependence of D values (Rajamani and Naldrett, 1978).
The partition coefficient of Ni between sulfide and silicate
liquids (DNi) is given by the equation:
(XNi)sulfide = DNi  (XNi)silicate, (1)
where ( XNi)sulfide and (XNi)silicate are Ni concentrations in the
sulfide and silicate liquids, respectively.
A more rigorous approach considers the exchange equilib-
ria for element pairs between coexisting phases. Equilibration
between sulfide liquid and olivine is expressed in terms of the
exchange coefficient for Fe and Ni (Boctor, 1982; Fleet and
MacRae, 1983, 1987, 1988; Fleet and Stone, 1990; Gaetani
and Grove, 1997; Brenan and Caciagli, 2000):
KD = (XNiS/XFeS)sulfide liquid/(XNiO/XFeO)olivine, (2)
where Xi is the mole fraction of the component i in the phase
of interest.
The extensive body of experimental measurements of this
parameter has been reviewed by Brenan (2003), who con-
cluded that KD increases with the Ni + Cu content of the
sulfide liquid phase and decreases with increasing oxygen
† Corresponding
author: e-mail, steve.barnes@csiro.au
*Present address: Physics of Geological Processes (PGP), University of
Oslo, P.O. Box 1048, 0316 Blindern, Oslo, Norway.
the Ni content of the sulfide phase introduces a nonlinearity
into the sets of equations that are commonly used to model
magmatic sulfide compositions in terms of silicate melt com-
position, D values, and R factor (silicate/sulfide mass ratio
at equilibrium). The implication is that Ni partitions more
strongly into already Ni-enriched sulfide, and this effect may
account for some of the more extreme Ni enrichment seen in
particular natural occurrences.
This contribution is an attempt to quantify the effect of
compositional dependence of KD and to apply it to model-
ing of unusually Ni rich primary magmatic sulfides in two
localities, the Mirabela intrusion in Brazil, and the komatiite-
hosted Betheno deposit at Yakabindie, Western Australia. In
both of these localities, large tonnage but low-grade orebodies
comprise 1 to 5% disseminated interstitial magmatic sulfide
assemblages hosted within coarse-grained, minimally altered
olivine-rich cumulates, and these two localities are ideal natu-
ral laboratories for investigation of olivine-sulfide equilibria.
Analytical Methods
Most of the data used in this study are derived from previ-
ous studies (Barnes et al., 2011a, b) but some new microprobe
data are reported here. New analyses of olivine, orthopyrox-
ene, and chromite were collected on Mirabela samples using
a Cameca SX50 electron microprobe at CSIRO, Australian
Resources Research Centre, Perth. An accelerating voltage
of 15 kV was used with a beam current of 30 nA, a spot size
of 1 µm, and counting times of 40 s for major elements and
100 s for minor elements (Ni, Zn, Cr). For the purposes of
oxygen barometry (as opposed to measurement of olivine/
sulfide equilibria) approximately six sets of analyses of the
three phases were collected per thin section for each sample,

0361-0128/13/4174/1971-12 1971
1972 BARNES ET AL.

using neighboring grains analyzed approximately 20 to 50 µm
from mutual grain boundaries. Oxygen barometry and geo-
thermometry were carried out using a spreadsheet supplied
by C. Ballhaus, based on the calibration reported by Ballhaus
et al. (1991) at a pressure of 3 kbars, with ferrous/ferric iron
ratios in spinel determined by stoichiometry. Nickel contents
of olivines used in the KD calculation for the Mirabela samples
were taken from the previously published study by Barnes et
al. (2011b), using the JEOL-JXA 8200 WD/ED microprobe at
the University of Oulu, Finland. Precision on Ni in olivine from
these analyses is estimated at ±250 ppm (2σ) at 2,500 ppm.
KD values were determined from measurements of Ni con-
tents of the cores of grains to avoid local Ni enrichment within
the outer 50 µm of olivines in contact with sulfides. Sulfide
compositions were estimated using the corrected whole-rock
assay data for Ni and S as described by Barnes et al. (2011b),
with estimated precisions on Ni in sulfide of 15% of the esti-
mated value (2 × relative standard deviation). Olivine and
sulfide compositional data on Betheno samples, and composi-
tional data on olivine in a single Mirabela sample, were deter-
mined by X-ray fluorescence microscopy (XFM), using the
Maia detector (Kirkham et al., 2010) on the XFM beamline at
the Australian Synchrotron (Paterson et al., 2011), using a
17.5-keV X-ray beam focussed to a 2- × 2-µm spot size. On-
the-fly scanning was employed and data collected in event
mode as described by Ryan et al. (2010); in these studies a
pixel size of 2 µm and a per pixel dwell of 0.488 msec were
Nickel tenors of the sulfides range from 15 to 25 wt %,
exceptionally high for rocks with relatively low values of the
MgO/(MgO + FeO) ratio (typically around 0.85) and are
closer to the typical values observed in komatiite-hosted
deposits, although Cu tenors (typically 5−8 wt %) are much
higher than komatiite values. Barnes et al. (2011b) concluded
that the observed pattern of sulfide tenor and silicate mineral
composition variations could not be explained by simple frac-
tionation within a closed-system magma chamber, and that
the ore zone represented a prolonged mixing event between
an initially S-undersaturated resident high Mg magma and a
sulfide-charged, cooler and lower Mg magma influx.
Olivines within the Santa Rita zone have Ni in the range
of 2,500 to 4,500 ppm with a median value of 3,200 ppm at
Fo84−88 (Fig. 1). Olivines within the ore zone have very similar
chemistry to those from unmineralized dunites in the under-
lying rocks (as inferred from whole-rock data on sulfide-free
olivine adcumulates, in the absence of microprobe data on
these rocks), fall within the upper part of the range of typical
layered intrusion olivines of this forsterite content (Yang and
5000
R=1000
4000
Ni ppm

used to produce the final high definition maps. Absolute Ni

measurements were calibrated to match electron microprobe S-free
R=500
data on Betheno olivines collected at Macquarie University, 3000 Kom
R=1000
Sydney, as described by Barnes et al. (2011a). Uncertainties
on ratios used to calculate KD values were determined using Mirabela
dunite R=500
the standard error propagation formula, where the sum of the 2000
relative standard deviation (RSD) of the ratio is the sum of the Layered
Intrusions
RSD of numerator and dominator.
R=100
1000 R=100
Localities
R=40 R=40
The Santa Rita (Mirabela) deposit
0
The Santa Rita ore zone within the Fazenda Mirabela intru-
sion is an unusual example of high-tonnage magmatic Ni-Cu- 80 85 90 95
PGE sulfide mineralization developed as a stratiform layer Fo mol %
within the main cumulus sequence of a layered intrusion, a Betheno olivine cores Betheno olivine rims
2.0-Ga-old intrusion in Bahia province, northeastern Brazil
Mirabela (Santa Rita zone) Model HMB QFM
(Barnes et al., 2011b). The intrusion as a whole is about 4 ×
2.5 km in outcrop dimensions and at least 3 km in original Mirabela sulfide-free dunite Model Kom QFM
maximum stratigraphic thickness. The resource estimate as of Sulfide-free komatiites Layered intrusions
November 2010 is 121 million metric tons (Mt) at 0.60 wt %
Ni, 0.16 wt % Cu, 0.016 wt % Co, and 91 ppb Pt. The ore zone Fig. 1. Olivine Ni vs. Fo (mol % MgO/[MgO + FeO]), for samples from
comprises a 50- to 200-m-thick interval containing up to 5 wt % Betheno and Mirabela, with data from Barnes et al. (2011a, b). Points
disseminated sulfides within a sequence of mostly unaltered labeled “Model Kom QFM” and “Model Kom HMB” are calculated compo-
harzburgites and orthopyroxenites. This orthopyroxene-dom- sitions of olivine generated by the modeling described in this paper for kom-
inated sequence lies between the dominantly olivine rich atiitic and komatiitic high Mg basalt starting compositions, respectively.
“Mirabela sulfide-free dunite” is the 80th percentile data density contour on
cumulates that comprise the lower part of the intrusion and whole-rock analyses of approximately 400 sulfide-free adcumulate dunites
the gabbroic cumulates that make up the upper part. Consis- (S <0.05, Al <10,000 ppm, Cu <0.02%) from the Santa Rita mine database
tent patterns of sulfide tenor—gradually decreasing Ni, near- (Barnes et al., 2011b). “Sulfide-free komatiites” field is 80th percentile den-
constant Cu, and gradually decreasing PGEs with generally sity contour on olivines from unmineralized komatiites, including barren
portions of the Agnew-Wiluna dunite bodies (data from Barnes and Fioren-
low PGE tenors—are found within the Santa Rita ore zone tini, 2012). “Layered intrusions” field is 80th percentile data density contour
across the entire intrusion and display relatively little lateral on unpublished data compilation of layered intrusion olivines by Yang and
variability. Maier, University of Oulu.
 SULFIDE-OLIVINE Fe-Ni EXCHANGE AND ANOMALOUSLY Ni RICH MAGMATIC SULFIDES 1973

Maier, unpub. comp.), and compare with the Ni-rich olivines
identified in some plume-related basaltic magmas (Sobolev et
al., 2005, 2007).
The Betheno deposit
Betheno is one of a series of low-grade but high Ni tenor
disseminated sulfide deposits hosted within extremely olivine
rich komatiitic dunites in the Agnew-Wiluna belt, in the
northern part of the Kalgoorlie terrane of the Archean East-
ern Goldfields superterrane of the Yilgarn craton (Groves and
Keays, 1979; Barnes, 2006; Grguric et al., 2006). These depos-
its are hosted within a series of lenticular bodies, each several
hundred meters thick and 500 to 2,000 m wide, primarily
composed of extreme olivine adcumulates. Mineralization
takes the typical form of broad zones of homogeneous low-
grade disseminated sulfides interstitial to original annealed
olivine crystals 2 to 20 mm diameter. Grades are typically very
consistent at around 0.6 to 1.0 wt % Ni. The Betheno deposit
forms a part of the Yakabindie cluster of deposits, with an
aggregate resource of 289 Mt at 0.58% Ni (Barnes and Fio-
rentini, 2012), but no separate resource estimate on the
Betheno lens itself is available. The deposit contains zones of
completely fresh, unserpentinized dunite with disseminated
sulfide mineralization. Sulfide assemblages in both fresh and
serpentinized intervals are extremely Ni rich, up to 34 wt %
Ni, and comprise aggregates of pentlandite and pyrite with
minor millerite. These assemblages are interpreted as the
result of low-temperature unmixing of essentially pristine
magmatic compositions. Sulfide tenors have been measured
using X-ray fluorescence mapping of entire thin sections; this
method gives the relative proportions of the component
phases of pentlandite, pyrite, and millerite. The bulk tenor is
then determined by combining measured (microprobe)
analyses of pentlandite with assumed stoichiometric pyrite
and millerite; values obtained agree with estimates based on
Ni-S whole-rock regression and have an estimated uncer-
tainty of ±10% of amount present. Olivine compositions are
highly magnesian (Fo93−94.5) and have Ni in the range 2,500
to 5,000 ppm (Fig. 1), with the higher values attributable to
reverse zoning toward higher Ni values in the outer rims
(Barnes et al., 2011a).
Sulfide-Olivine KD Values
Brenan (2003) collected and compiled a body of data on
Fe/Ni sulfide/olivine KD (eq. 2) as a function of temperature,
sulfide composition, and fO2, and concluded that KD increases
with the Ni + Cu content of the sulfide liquid phase and
decreases with increasing oxygen fugacity. To account for the
interdependence of temperature and fO2, we have recast the
experimental database in terms of fO2 relative to the quartz-
fayalite-magnetite (QFM) oxygen buffer (Fig. 2).
Experimental results (Brenan and Caciagli, 2000; Brenan,
2003) were used to calculate variation of KD as a function of
Ni concentration in the sulfide melt and oxygen fugacity recal-
culated as ΔQFM, where ΔQFM is calculated as follows:
ΔQFM= log(fO2T) − log(fO2QFM(T)), (3)
with fO2T defined as the oxygen fugacity at the temperature
of the experiment and (fO2)QFM(T) the corresponding oxygen
fugacity at the temperature of the QFM buffer.

60

50
-1
=

40
M
F

0
Q

30
=
Kd

M
F

1
Q

20
=
M
F
Q

10

0
−3
−2 40
−1 30
QF 20 e
M 0 ) in sulfid
10
N i (wt%
1 0
Fig. 2. Best fit polynomial surface to experimental data compilation of Brenan (2003) with fO2 expressed as log units above
or below QFM at the temperature of the experiment. Error bars are 2σ uncertainty of calculated KD values; uncertainties on
Ni in sulfide and fO2 not reported but likely to be small compared to those on KD.
1974 BARNES ET AL.

The relationship between measured KD, sulfide melt com-
positions, and calculated ΔQFM was evaluated by fitting a
plane (a polynomial equation weighted with measured errors
on KD) to the experimental dataset (Fig. 2) and is given by:
KD = a + b * CNi3 + c * ΔQFM, (4)
Table 1. Coefficients and Uncertainty for Polynomial Regression of
Experimental Measurement of KDFe/Ni(olivine/sulfide) (eq 4)
ΔQFM = difference between log fO2 of experiment and that of QFM buffer
at the same temperature
where KD = a + b(wt % Ni in sulfide)3 + cΔQFM

where a, b, and c are constants (Table 1) and CNi is the Ni con-
centration in the sulfide melt. Correlation coefficient for the
regression (R2) is 0.83 with errors in a, b, and c given in Table
1. These values were used to calculate errors in the KD versus
Ni curves at a given ΔQFM (Fig. 3).
The projected curves for KD versus sulfide composition are
then plotted for the QFM fO2 buffer, for one log unit above
and one and two log units below (Fig. 3). The range of error
in KD is plotted as the shaded gray field around the QFM+1
curve and is based on a “worst case” combination of 2σ errors
of a, b, and c. These curves are compared with values of KD
as determined for a suite of samples from the Santa Rita ore-
body and for a single sample of fresh dunite from Betheno
(see Barnes et al., 2011b, for details of the methodology).
The KD values are based on bulk compositions of the sulfide
phase determined as described above and compositions of the
homogenous olivine cores. The Mirabela data set straddles
the QFM+1 curve, but given the range in the data and the
uncertainty in the polynomial fit to the data, the results are
consistent with equilibration of olivine and sulfide liquid at or
close to QFM. The Betheno sample also straddles the QFM
and QFM+1 curve within the 2σ error in KD, which arises
from the wide variability in Ni content of olivine rims in the
Coefficient value 2σ error
with a 13.95 1.96
b 0.00037 0.00002
c −4.10 0.98
R2 = 0.828271
samples studied. Significantly, both deposits fall on the por-
tion of the KD composition curve where KD shows a strong
positive dependence on composition.
An additional uncertainty in the Ni content of the sulfide
liquid is introduced by uncertainty in the original oxygen con-
tent of the sulfide liquid. The magnetite content of the dis-
seminated sulfides at both Betheno and Mirabela is low but
may have been lowered by loss of O from the sulfide melt
during solidification (Naldrett, 1969). However, the O solubil-
ity in sulfide mattes has a strong negative dependency on the
combined Ni and Cu contents of the matte (Fonseca et al.,
2008), and for the very Ni rich sulfide compositions reported
here is likely to be considerably less than 10% and probably
less than 5%. The uncertainty in KD is therefore small and
within the error of variability of Ni in both phases.

35

30
KD = (NiS/FeS) sulfide / (NiO/FeO) olivine

-2
25 QFM
-1
QFM
20
M
QF
+1
M
QF
15

10 Stillwater
Maine gabbros
Jinchuan
5 Voisey's Bay
Betheno
Mirabela
0
0 5 10 15 20 25 30 35 40

Wt % Ni in sulfide melt
Fig. 3. Natural data from Betheno and Mirabela plotted on projections of polynomial three-dimensional surface for QFM
buffer, and QFM ± one log unit. Gray shaded field shows 2s uncertainty on position of the QFM+1 curve based on the
three-dimensional regression data. Data are also shown for Voisey’s Bay (Li and Naldrett, 1999), Jinchuan (Chai and Naldrett,
1992), Stillwater JM reef and Maine gabbros (Thompson et al., 1984) from data compilation of Brenan (2003).
 SULFIDE-OLIVINE Fe-Ni EXCHANGE AND ANOMALOUSLY Ni RICH MAGMATIC SULFIDES 1975

Estimation of fO2
The fO2 conditions of equilibration in the Mirabela samples
have been estimated using the spinel-olivine-orthopyroxene
geobarometer developed by Wood (1990) and calibrated by
Ballhaus et al. (1991). Data were collected on samples, in
all cases by analyzing chromite, orthopyroxene, and olivine
within about 100 µm of triple point contacts (Fig. 4). Ferric
iron in chromite was calculated assuming stoichiometry. Data
are presented in the supplementary materials associated with
this paper, and details of analytical methods can be found in
Barnes et al. (2011b).
Results are plotted in Figure 5. Oxygen fugacity is estimated
at close to or just above the quartz-fayalite-magnetite (QFM)
buffer, at subsolidus blocking temperatures of around 600°C.
The plot also shows the effect of allowing for Fe-Mg exchange
between olivine and chromite during subsolidus cooling, in
an attempt to unwind this effect and estimate the fO2 that
would have applied at the crystallization temperature. The

2 mm
pn

py

(B)
ch
pn
po
olivine

opx

A NiFeCr
6000

Ni ppm
4000

olivine
2000 Traverse 2
Tr
ave
C Traverse 1 rs
0 e
1200 800 400 0 2

6000 Ni ppm olivine

4000
1
se
er
av
Tr

2000
opx
0
C Traverse 2 B
600 500 400 300 200 100 0 Ni abundance map (log)
Distance from olivine-sulfide contact, microns
Fig. 4. X-ray fluorescence microscopy maps collected using the Maia 384 detector on the XFM beamline at the Australian
Synchrotron (Paterson et al., 2011). A. Map of approximately one-quarter of a standard thin section, scan area is 13.5- ×
7.0-mm or 6,750 × 3,500 2-µm pixels. RGB three-element map with Ni (red), Fe (green), and Cr (blue). Phases: ch = chro-
mite, opx = orthopyroxene. pn = pentlandite, po = pyrrhotite. B. Map of (log transformed) Ni content for indicated subregion
of (A). C.-D. Profiles of measured Ni content (from XFM maps) along traverses 1 and 2 indicated in (B). High Ni end of
traverse corresponds to olivine-sulfide contact.
B
1976 BARNES ET AL.
-9
-11
-13
log f O2
-15
-17
-19
-21
-23
500 700 900 1100
T °C
Fig. 5. fO2-T plot for Mirabela chromite-olivine-opx geobarometer
(method of Ballhaus et al., 1991). Solid line = QFM buffer, dashed line =
path of calculate oxygen fugacity during exchange of Fe and Mg between
olivine and spinel, assuming constant Fe/Mg in olivine and constant Fe3+
content of spinel, simulating the effect of subsolidus equilibration between
these phases.
“exchange” curves show the effect of varying the MgO/FeO
ratio in the chromite, keeping all other variables constant, and
recalculating the equilibration temperature and fO2 as a func-
tion of this change. This involves two underlying assumptions.
First, chromite is a trace phase in the rock, so that the change
in Fe/Mg in olivine accompanying this reequilibration is neg-
ligible, all the change being accommodated in the chromite.
Second, chromite is the dominant reservoir of Fe3+ between
the phases involved, so Fe3+ in chromite can be assumed not
to change during Fe/Mg exchange. The results of this calcu-
lation indicates that the reequilibration follows a T- fO2 path
nearly parallel to that of the QFM buffer, and the subsolidus
equilibrium is a reasonable guide to the oxidation state of the
magma. Uncertainties in temperature are likely to be on the
order of tens of degrees (Kessel et al., 2007), which would
introduce an error of up to one log unit in the estimated fO2.
We conclude that magmatic olivine-sulfide equilibrium took
place at oxygen fugacities within a log unit of QFM. The low
blocking temperature raises the question of the effect of sub-
solidus reequilibration between olivine and sulfide: this is
considered below.
Modeling Sulfide Liquid Compositions with
Composition-Dependent KD Values
The olivine-sulfide Fe-Ni equilibrium equation (4) applies
regardless of the presence or absence of silicate liquid, so
this relationship can be used to determine the distribution of
Fe and Ni in three phase mixtures of olivine, sulfide liquid,
and silicate liquid, with some additional assumptions. Mod-
eling of magmatic sulfide compositions commonly involves
the assumption of simple bulk equilibrium crystallization and
constant partition coefficients (Campbell and Naldrett, 1979;
Lesher and Burnham, 2001). Incorporating olivine into the
system requires a method that solves for equilibrium distribu-
tion of elements such as Ni, Cu, Mg, and Fe between given
proportions of coexisting olivine, sulfide liquid, and silicate, at
constant bulk composition of the system. Solving for composi-
tions of silicate melt, olivine, and sulfide with the additional
complication of compositional dependence of KD requires an
iterative approach (Fig. 6), owing to the nonlinearity of equa-
tions describing Fe-Ni distribution.
The modeling addresses the scenario where a fixed propor-
tion of Ni-free FeS liquid is added to an equilibrium assem-
blage of olivine and silicate liquid and calculates the effect
of exchange of Fe and Ni between all three phases, as Ni is
taken up by the sulfide phase. Equilibrium between the three
phases is modeled by first calculating the olivine composition
that would be in equilibrium with the silicate melt while hold-
ing the composition of the silicate and sulfide melts constant,
then calculating the equilibrium value of the sulfide melt,
holding the olivine and silicate melt compositions constant.
Olivine composition is calculated at each step using the
well-established Roeder and Emslie (1970) relationship for
the Mg/Fe KD between olivine and silicate melt, as modi-
fied by Herzberg and O’Hara (2002) to give the following
expression:
Kd(Mg/Fe)(olivine/liquid) = 0.382 − 0.0164 DMgO(olivine/liquid), (5)
where DMgO(olivine/liquid) is the partition coefficient for MgO
between olivine and silicate liquid.
Nickel partitioning between olivine and the silicate melt is
described by the following composition-dependent partition
coefficient:
DNi(olivine/liquid) = −3.665 + 3.346DMgO(olivine/liquid), (6)
after Beattie et al. (1991). Li and Ripley (2010) provided a
more recent and more rigorous parameterization, but this
requires more detailed knowledge of silicate melt composi-
tion than we wish to assume; equation (6) requires values for
MgO and FeO only and provides sufficiently close agreement
for komatiitic and high Mg basaltic compositions for the pur-
poses of this calculation.
The calculation takes as its input values for MgO, FeO, and
NiO in the initial silicate liquid (Table 2), using typical values
for komatiite, komatiitic basalt and tholeiitic basalt estimated
from a comprehensive data compilation of Archean komatiites
and tholeiites (Barnes et al., 2012b), a value for the mass frac-
tion of olivine in the system, and a value for mass ratio R of
Table 2. Starting Compositions for Modeling
Komatiite HMB Tholeiite
MgO 30.0 14.0 8.0
FeO 10.0 12.0 10.0
NiO 0.2 0.06 0.015
Olivine Fo 94.2 86.3 81.2
Olivine Mg 52.5 46.4 43
DNiOl 2.18 7.40 14.28
KdFeMgo 0.35 0.33 0.29
Notes: HMB = high Mg (komatiitic) basalt starting liquid, 14% MgO
 SULFIDE-OLIVINE Fe-Ni EXCHANGE AND ANOMALOUSLY Ni RICH MAGMATIC SULFIDES 1977

Set initial silicate liquid composition
and proportion of olivine and (initially
Ni, Cu free) sulfide liquid
Calculate initial olivine and
approximate sulfide composition
from starting silicate composition
Calculate bulk composition of whole
system
Calculate new olivine composition
from current silicate sulfide
Is mass
balance
satisfied?
yes
Calculate FeNi KD and hence new Ni,
Fe and Cu content of sulfide liquid
and olivine based on current estimate
of olivine and silicate melt
Is mass
balance
satisfied?
yes
updated by assuming that the effects of any mass which needs
to added or removed to the system are partitioned between
the compositions of the silicate and the changing phase
(either olivine or sulfide) according to the partition and dis-
tribution coefficients defined above. Once the mass-balance
condition is satisfied, the current input value for Ni in sulfide,
Nisul0, is compared with a new value, Nisul1 derived from the
value of KD (eq. 2, 4) determined by Nisul0 and the current
estimate of olivine composition. Where Nisul0 and Nisul1 agree
Update silicate within accepted tolerance (0.05 wt %), the solution has been
melt composition reached; otherwise the value of Nisul0 is adjusted to the aver-
to satisfy mass
age of the previous closest too high and too low values, and
balance
the iteration is repeated (Fig. 6).
The calculation was performed using an Excel spreadsheet
no over a range of R values for three different silicate melts: a
komatiite, a nickel-rich high Mg basalt, and a tholeiitic basalt
(see Table 1 for starting compositions), olivine, and sulfide liq-
uid, with the mass fraction of olivine in the system held at 5%
relative to silicate melt fraction at 100% for all runs except
Update silicate where indicated. Results of selected calculations are given in
melt composition Table 3 and shown in Figures 7 and 8 for sulfide melt compo-
to satisfy mass sitions, and Figure 1 for olivine compositions.
balance
The magnitude of the KD effect can be seen by compar-
ing the Ni-R curves (Fig. 7) for the composition-dependent
no
model with the curve for constant values of DNi (sulfide/silicate).
Results are shown for values of R ranging from 40, corre-
sponding approximately to the typical sulfide abundance seen
in disseminated Ni ores in komatiitic dunites (Barnes, 2007),
up to 1,000. The model shows that at low R factors, where Ni

no
40
Are compositions of Thol Basalt variable KD QFM
silicate, sulfide, olivine all Thol Basalt constant D = 400
35
consistent with D and KD Komatiite constant D=200
values? Komatiite variable KD QFM+1
30 Komatiite variable KD QFM
Kom Bas constant D = 300
yes 25 Kom Bas variable KD QFM 5% olivine
Ni in sulphide %

Solution reached Kom Bas variable KD QFM 20% olivine

20
Fig. 6. Flow chart showing calculation procedure for modeling of sulfide,
olivine, and silicate melt equilibria using composition dependent KD for Fe
and Ni between olivine and sulfide. 15

silicate to sulfide liquid (Campbell and Naldrett, 1979). The
initial bulk composition is calculated as the bulk combination
of combined silicate melt and given mass fraction of olivine
with a composition calculated to be in equilibrium with the
starting silicate melt and is hence richer in MgO and NiO than
the initial assumed melt composition. The first estimate of
sulfide Ni content is taken to be that derived from the given R
value, starting Ni in silicate, and an estimate of DNi(sulfide/liquid)
taken to be 200 for komatiite, 300 for high Mg basalt, and 400
for tholeiitic basalt based on experimental and empirical val-
ues (Barnes and Lightfoot, 2005). A series of subsequent iter-
ations than adjusts this preliminary estimate to converge on a
solution, as described in the flowchart in Figure 5.
After calculating a new composition for either the olivine
or the sulfide, the silicate composition needs to be adjusted
to satisfy mass-balance constraints. The silicate composition is
10
5
0
10 100 1000
R factor
Fig. 7. Result of model calculations. Plots of calculated Ni in sulfide liq-
uid using starting compositions in Table 1. Model assumes initial 5% olivine
except where stated, and sulfide liquid with zero initial Ni content, and solves
for equilibrium Ni S, Cu, Fe, and Mg distribution among the three phases for
different values of R and constant bulk composition, using the composition
dependence of KD along the QFM and QFM+1 oxygen buffer line shown in
Figure 1 (curves labeled “variable KD”). “Constant D” curves ignore com-
positional dependence of KD and assume constant values of DNi(sulfide/silicate) of
200 for komatiite, 300 for komatiitic basalt (“Kom Bas”), and 400 for tholeiitic
basalt (“Thol Basalt”), based on temperature dependence of this parameter
determined by Rajamani and Naldrett (1978).
1978 BARNES ET AL.

Table 3. Output from Model Calculations

Starting comp fO2 buffer KD Fol R NiOl NiSul Fo Ol

Kom30 QFM 14.0 0.05 40 355 5.0 93.8

Kom30 QFM 14.8 0.05 100 820 13.3 93.8
Kom30 QFM 29.5 0.05 500 2051 34.9 93.8
Kom30 QFM 39.7 0.05 1000 2632 42.4 93.8
Kom30 QFM 14.6 0.005 100 796 12.2 93.8
Kom30 QFM 27.4 0.005 500 1990 33.2 93.8

Kom30 QFM+1 9.9 0.05 40 479 4.8 93.8

Kom30 QFM+1 10.5 0.05 100 1043 12.3 93.8
Kom30 QFM+1 20.9 0.05 500 2236 31.1 93.8
Kom30 QFM+1 30.2 0.05 1000 2696 39.1 93.8

HMB 14 QFM 14.0 0.05 40 286 2.4 86.4

HMB 14 QFM 14.1 0.05 100 670 5.3 86.4
HMB 14 QFM 17.3 0.05 500 1794 13.9 86.4
HMB 14 QFM 18.4 0.05 1000 2610 17.0 86.4
HMB 14 QFM 14.0 0.2 40 505 4.0 86.4
HMB 14 QFM 14.1 0.2 100 1077 6.9 86.4
HMB 14 QFM 15.4 0.2 500 2320 17.1 86.4
HMB 14 QFM 15.6 0.2 1000 2970 19.3 86.4

HMB 14 QFM+1 9.9 0.05 40 601 3.5 86.4

HMB 14 QFM+1 10.0 0.05 100 1312 7.3 86.4
HMB 14 QFM+1 11.3 0.05 500 3412 17.5 86.4
HMB 14 QFM+1 12.8 0.05 1000 4169 21.2 86.4

Thol8 QFM 13.9 0.05 40 116 0.7 83.0

Thol8 QFM 13.9 0.05 100 248 1.4 83.0
Thol8 QFM 14.0 0.05 500 870 5.0 83.0
Thol8 QFM 14.0 0.05 1000 1174 6.5 83.0
Thol8 QFM 14.0 0.005 100 179 1.2 83.0
Thol8 QFM 14.0 0.005 500 657 4.0 83.0

Thol8 QFM+1 9.8 0.05 40 116 0.6 83.0

Thol8 QFM+1 9.8 0.05 100 376 1.6 83.0
Thol8 QFM+1 9.9 0.05 500 1020 3.7 83.0
Thol8 QFM+1 9.9 0.05 1000 1334 5.1 83.0

Thol8 QFM-2 22.1 0.05 100 184 1.9 83.0

Thol8 QFM-2 22.2 0.05 500 688 6.3 83.0
Thol8 QFM-2 22.3 0.05 1000 1037 8.5 83.0

Notes: NiOl = Ni ppm in olivine; NiSul = wt % Ni in sulfide liquid; Fo Ol = forsterite content of olivine, molar %; HMB 14 = high Mg (komatiitic) basalt
starting liquid, 14% MgO; Thol8 = tholeiitic basalt starting liquid, MgO = 8%

tenors are low, there is little difference between the constant
D and variable KD curves. However, as Ni tenors begin to rise
at higher R values, the curves begin to diverge significantly,
particularly for the komatiite composition. Constant D curves
are substantially lower for the komatiite case, predicting sul-
fide tenors around 22% compared with 34% at R = 500. The
effect is negligible for the tholeiitic basalt composition, but sig-
nificant divergence is observed for the high Mg basalt model.
This model, a komatiitic basalt composition with a somewhat
elevated, stated Ni content of 600 ppm, is selected to account
for the Ni-rich olivines at Mirabela and gives a good fit to the
Mirabela sulfide compositions. The model also reproduces
the observed sulfide and olivine compositions at Betheno with
an R value around 500, consistent with independent estimates
based on PGE tenors of the sulfides (Barnes et al., 2012a).
The calculation is relatively insensitive to the assumed mass
of olivine in the models; changing the initial mass fraction of
olivine to 0.5% rather than 5% (relative to fixed silicate melt
proportion of 100%) with other factors held constant reduces
the resulting sulfide Ni content by about 0.5 to 1 wt % for
the komatiite case. In the high Mg basalt “Mirabela” case, the
effect is somewhat larger. Increasing the original olivine per-
centage from 5 to 20% increases the final Ni content of the
sulfide at R value 1,000 from 17.0 to 19.3 (Fig. 7). This effect
arises because the bulk Ni content of the system is higher
where the initial olivine content is higher, as originally pointed
out by Lesher and Burnham (2001), and the effect is larger for
the basalt than the komatiite case because the DNi for olivine/
melt is higher for the basalt than the komatiite.
Results of the komatiite model are plotted in Ni-Ir compo-
sitional space in Figure 8, to show how the model accounts
for Ni variability in relationship to PGE content in sulfide.
The blue, green, and purple curves are simple R-D mod-
els, using the standard equation of Campbell and Naldrett
(1979), assuming various combinations of constant D values
for Ir of 10,000 and 100,000 and for Ni of 150 and 250, and
assuming starting komatiite magma compositions of 1 ppb Ir
and 1,600 ppm Ni. These are compared with estimated bulk
 SULFIDE-OLIVINE Fe-Ni EXCHANGE AND ANOMALOUSLY Ni RICH MAGMATIC SULFIDES 1979
1000
D Ir 10K D Ni 150
R=200
R=200
Ir ppb in sulfide
R=100
R=100
R=50
100
R=40
R=20
0 10
Ni wt. percent in sulfide
Fig. 8. Bulk compositions of komatiite-hosted magmatic sulfide ores, expressed as Ir vs. Ni in 100% sulfides, compared
with model curves for various combinations of silicate/sulfide liquid partition coefficients for Ir and Ni, and with the model
curve (red) generated by the model described in this study. Ore compositions from compilation of Barnes et al. (2012a).
Model curves assume starting composition of 30%, 1,600 ppm Ni and 1 ppb Ir
compositions of komatiite-hosted sulfide ores, from the com-
pilation of Barnes et al. (2012a). The outlying Betheno data
point is considerably higher for given Ir content, and at con-
stant D would require a DNi value of 500. The variable kD
model accounts for the Betheno composition and shows how
extremely high Ni values can be reconciled with moderate
PGE contents that preclude exceptionally high R values.
Discussion
Effect of subsolidus equilibration
The low temperatures indicated by the spinel-olivine-
orthopyroxene equilibria at Mirabela raises the question of
the effect of subsolidus reequilibration between olivine and
sulfide liquid. In particular, it is important to assess whether
the high Ni tenors could be the result of subsolidus diffu-
sion of nickel out of olivine and into sulfide. This question
was considered in detail for the Betheno case by Barnes et al
(2011a), who showed that olivines there have homogeneous
cores with respect to Ni but showed a distinct Ni enrichment
at the margin. (This variability accounts for the large uncer-
tainty in the calculated KD for Betheno shown in Fig. 3). Oliv-
ines apparently gained some Ni from the sulfide during late
stage reequilibration. This implies a slight decrease in the KD
toward lower temperatures in this setting, which would tend
to decrease the Ni content of sulfide slightly. Crucially, this
observation implies that the Ni sulfide tenor was reduced,
not increased, as a result of subsolidus diffusion. However, it
appears that the effect of subsolidus reequilibration is negli-
gible, as the sulfide tenors of the present sulfide assemblage
closely match those predicted from whole-rock Ni-S regres-
sion: the regression estimate gives the original composition of
the cumulus sulfide fraction and agrees within 2% (absolute
value) of the tenor estimate from XRF mapping (Barnes et
al., 2011a).
In the Mirabela case, olivine also shows a distinct enrich-
ment in Ni over a zone approximately 100 to 150 µm wide
immediately adjacent to sulfide blebs, as shown in X-ray
R=500
DIr 100K
DNi 250 DIr 10K
DNi 250 R=250
D Ir10K, composition
dependent Fe/Ni KD
Betheno
Kambalda
Mt. Keith
Other komatiite
20 30 40
fluorescence microscopy maps and profiles (Fig. 4). (Haloes
of apparent enrichment in an element adjacent to a phase
very rich in that element, as in this case of olivine next to pent-
landite, can be an artefact of sloping grain boundaries and
excitation of Ni X-rays from sulfide beneath olivine within the
sampled volume, but this is unlikely here, as olivine enrich-
ment is seen at too high a proportion of olivine-sulfide and
pyroxene-sulfide boundaries for this to be a fortuitous effect
within a 30-µm-thick sample). Olivine cores more than 100 µm
away from sulfide contacts appear to be extremely homoge-
neous. As in the Betheno case, subsolidus equilibration cor-
responds to a decrease in the KD value by as much as 50%, but
the volume of olivine affected by this process is very small, as
indicated by the following calculation. A 100-µm rim on a
1-mm-diam olivine crystal represents 23% of the volume of
the grain, but only about 2% of the olivine in the sample is in
contact with sulfide; hence the relative proportion of “Ni-
enriched” olivine is about 2.5%, or roughly half the proportion
of sulfide in the rock. Assuming this olivine contains an excess
of 1,500 ppm Ni, this is equivalent to less than 0.5% of the
original Ni present in sulfide, well within the limit of uncer-
tainty of the tenor estimate.
The highly restricted nature of subsolidus equilibration of
Fe and Ni between olivine and sulfide is puzzling, in view
of the widespread evidence for subsolidus equilibration of
silicates and silicate-spinel pairs in most slowly cooled igne-
ous rocks. The following explanation is offered. For the very
Ni rich sulfides under consideration, the exchange reaction
at low temperature is no longer with an FeNiCuS melt, but
with a solid assemblage containing pentlandite and pyrrho-
tite. Pentlandite, possibly the high-temperature form (Kita-
kaze and Sugaki, 2004), would have been a stable phase below
about 800°C, so that the exchange reactions of interest would
have been between pentlandite, pyrrhotite, and olivine. Pent-
landite has a relatively restricted compositional range, such
that the activity of NiS would be essentially fixed in the sul-
fide component once pentlandite appears. Hence further
Fe-Ni exchange between olivine and sulfide would be limited
1980 BARNES ET AL.
at the temperatures recorded by the spinel-olivine blocking
temperature.
Regardless of this additional factor, subsolidus reequilibra-
tion could not have had a significant impact on the Ni tenor of
the sulfide in either locality described here, where the sulfide
fraction is the dominant reservoir of Ni in the rock. The sul-
fide composition is essentially locked in under magmatic con-
ditions, and while subsolidus effects may subsequently modify
the KD value and the olivine composition, the effect appears
to be negligible. The high-temperature sulfide Fe/Ni KD is
unaffected by low-temperature equilibration.
Ni-rich parent magmas
The composition dependence of KD, and hence the effec-
tive Ni partition coefficient, combined with high Ni contents
in the parent magma, is the critical factor in generating excep-
tionally rich Ni sulfides at Betheno and Mirabela. However,
it is necessary to consider alternative mechanisms that may
have led to exceptional Ni enrichment, such as derivation
from unusually Ni rich magmas. Possible mechanisms for Ni
enrichment in parent magmas include upgrading due to dis-
solution of previously formed sulfide liquids (Kerr and Leitch,
2005), or generation of anomalously Ni-rich magmas from
pyroxenitic mantle sources (Sobolev et al., 2007). Anomalous
Ni contents in magmas should be manifest in unusually high
Ni in olivine, but as is evident from Figure 1, the olivine cores
at Betheno fall within the typical range of Ni contents for
unmineralized komatiites. In the Betheno case, there is no
need to appeal to anything other than typical Ni contents for
komatiitic magmas, and hence no evidence for anomalously
Ni-rich magmas. In both the Betheno and Mirabela cases,
the olivines in the disseminated ores are not detectably dif-
ferent from those in adjacent unmineralized rocks, or in other
unmineralized rocks of their general magma type (Fig. 1). This
is essentially a consequence of R factors being high enough to
overcome any significant depletion of Ni in the silicate phases
during sulfide equilibration, an effect which is quantified by
the model olivine compositons in Figure 1.
At Mirabela, however, the high Ni contents of the olivines
(Fig. 1), in the upper range for typical layered intrusion oliv-
ines of this forsterite range, do imply a somewhat Ni-rich par-
ent magma. Comparison with olivine data from the Sobolev et
al. (2007) data set suggests that the Mirabela parent magma
(or magmas) may have belonged to the category of magmas
derived from “pyroxenitic” mantle plume sources. These
magma have higher than normal Ni, by a factor of 1.5 to 2,
relative to normal tholeiites of similar Mg numbers, which
according to the Sobolev et al. (2007) interpretation is owed
to having pyroxene- as opposed to olivine-rich mantle sources.
The Ni contents of olivines within the Santa Rita ore zone are
very similar to the Ni contents of adcumulate dunites (nearly
pure olivine adcumulates) from outside the ore zone (Fig. 1,
red outline), indicating that high Ni magmas were a charac-
teristic of the ultramafic zone of the intrusion as a whole, not
only the ore zone. This has a number of implications: first,
the high Ni of the Mirabela olivines is inherited from the par-
ent magma and cannot be ascribed purely to interaction with
sulfides; second, the starting olivine compositions used in the
model calculations are reasonable and not biased by abnormal
olivine compositions within sulfide-bearing rocks; and finally,
the Santa Rita sulfide ores formed at high R values, such that
there was no detectable depletion of olivine in Ni due to com-
petition with sulfide liquid (see model olivine compositions in
Fig. 1). Regardless of the mechanism, however, the observed
olivine compositions at Mirabela, in both barren and miner-
alized rocks, combined with predicted KD values provide a
plausible explanation for explanation of the high Ni tenors.
The Kerr and Leitch (2005) model, for upgrading of origi-
nally “normal” magmatic sulfides as a result of partial disso-
lution in fresh magma, provides a possible explanation for
attainment of high Ni sulfides but is not considered to be a
significant effect in the present cases. The mechanism should
cause an upgrading in PGE tenors as well as in Ni—this is
not observed at Mirabela, where PGE tenors are characteris-
tically low, and completely decoupled from Ni, through most
of the Santa Rita ore zone. In the Betheno case, the PGE
tenors of the sulfide liquid are typical of those observed in
komatiitic ores, and at the neighboring Mount Keith deposit
(Barnes et al., 2011a, 2012a), implying that the mechanism
inducing anomalous high Ni did not result in corresponding
PGE enrichment. The PGE tenors of the Betheno and Mount
Keith sulfides can be reproduced by our KD-based model
(Fig. 8). Hence a process peculiar to Ni, such as that proposed
here, is preferred.
Implications for S solubility in silicate melts
The extremely high Ni contents of the Betheno sulfides
have implications for considerations of the sulfur content of
silicate melt at sulfide liquid saturation (SCSS). The Betheno
sulfides are approximately 50:50 mixtures of FeS and NiS;
hence the reactions determining the S content of the equi-
librium silicate melt are not only determined by FeO-FeS
activity relationships, as is commonly assumed, but also by
NiS-NiO equilibria. The Ni content of the silicate melt should
be as important in determining the SCSS as the Fe content.
This is consistent with the findings of Ariskin et al. (2013), and
also with observations on the effects of Cu in the silicate melt
on the solubility of Cu-rich sulfides (Ripley et al., 2002).
Exploration implications
Extremely Ni rich sulfides may be more common in nature
than has been hitherto assumed. The essential requirement
for Ni enrichment is that sulfide liquids equilibrate with at
least moderately Ni enriched melts under moderate to high R
factor conditions. The critical role of olivine in the process is
to increase the bulk availability of Ni in the system; effec-
tively, providing an additional source of Ni for the sulfide melt
to scavenge. This effect accounts for an additional 2 to 3% Ni
in the sulfide for the model high Mg basalt parent magma
where the initial olivine content is taken to be 20% (Fig. 7).
Because olivine contributes Ni but not Cu, this effect also
contributed to elevated Ni/Cu ratios in such cases. Hence,
the most likely environments for anomalously Ni-rich, high
Ni/Cu sulfide mineralization are disseminated ores formed
from olivine-saturated magmas in conduits or large layered
intrusions, containing a suspended load of olivine crystals.
The olivine load should be high enough to contribute addi-
tional Ni to the bulk composition of the system but not high
enough to affect the rheology to the point where high R val-
ues cannot be attained.
 SULFIDE-OLIVINE Fe-Ni EXCHANGE AND ANOMALOUSLY Ni RICH MAGMATIC SULFIDES 1981
Unusually Ni-rich sulfides may be generated without the
need for exotic magmas in cases of highly reduced magmas,
such as may occur where magmas have assimilated high
proportions of graphitic country rocks. Such ores may have
anomalously high Ni/Cu ratios, and this feature in dissemi-
nated ores should not necessarily be taken as an indication
that Cu has been hydrothermally stripped, unless indepen-
dent evidence exists (e.g., Gole, 2008). The high Ni tenors
commonly observed in altered komatiitic dunites, e.g., at
Dumont (Eckstrand, 1975) and Black Swan (Barnes et al.,
2009) are likely to be primary, notwithstanding the clear min-
eralogical evidence that the sulfide mineral assemblages have
equilibrated at low temperatures. Such deposits are poten-
tially valuable exploration targets, even in the absence of mas-
sive sulfide accumulations.
Conclusions
The nonlinearity of monosulfide solid solution at magmatic
temperatures results in positive dependence of KD on Ni con-
tent of the sulfide liquid phase. This dependency is a mani-
festation of a positive feedback: the more Ni rich a sulfide
liquid, the higher the tendency of Ni to partition into that
sulfide liquid. The consequence of this is that it is possible
to generate exceptionally Ni rich sulfide liquids from mod-
erately Ni rich magmas, where equilibration occurs at suffi-
ciently high R factors on the order of a few hundred. This
effect is most evident in komatiites and in mafic magmas that
crystallize Ni-rich olivines. In the case of less magnesian liq-
uids, anomalously Ni-rich sulfide liquids may be the hallmark
of magmas derived from pyroxenite-rich mantle sources, as
proposed by Sobolev et al. (2005, 2007). Anomalously reduc-
ing conditions in magmas may also give rise to unusually Ni
rich sulfides, owing to the dependency of the KD value on fO2
(Fig. 2). However, in both examples cited here, the Mirabela
intrusion and the Betheno dunite body, there is no need to
appeal to exotic oxidation states, and high Ni tenors can be
generated during sulfide-silicate-olivine equilibration close to
the QFM buffer, consistent with olivine-orthopyroxene-spinel
oxygen barometry on Mirabela samples. Highly Ni enriched
sulfides with anomalously high Ni/Cu ratios may be more
common in nature than is commonly recognized and do not
need to be explained by hydrothermal alteration processes.
Highly reducing conditions favor more Ni-rich sulfides, so
intrusions containing graphite derived by assimilation of black
shales may have high potential for Ni-rich disseminated sul-
fide mineralization.
Acknowledgments
We thank Mirabela Nickel NL for access to drill core
through the Mirabela intrusion and BHP Billiton for access to
Betheno. Greg Hitchen provided assistance with electron
microprobe analysis. Kathryn Spiers assisted with the X-ray
fluorescence mapping. We thank Chris Ryan, Martin de Jonge,
and Daryl Howard for assistance and support in the X-ray fluo-
rescence microscopy component of this research. Thanks are
also due to Shenghong Yang and Wolfgang Maier for access to
their compilation of data on layered intrusion olivines. This is
an output from the CSIRO Minerals Down Under National
Research Flagship. B. Godel and J. Robertson are funded by
the CSIRO Office of the Chief Executive Postdoctoral
Fellowship scheme. We thank Yulia Uvarova and Marcus
Sweetapple for constructive reviews of an early draft, and Eco-
nomic Geology reviewers Chusi Li and Simon Jowett for
detailed comments and suggestions. Part of this research was
undertaken on the X-Ray Fluorescence Microscopy (XFM)
beamline at the Australian Synchrotron, Victoria, Australia.
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