Mineralium Deposita (2004) 39: 523535
DOI 10.1007/s00126-004-0433-0
A RT I C L E
J. Arif T. Baker
Gold paragenesis and chemistry at Batu Hijau, Indoneisa: implications
for gold-rich porphyry copper deposits
Received: 15 January 2004 / Accepted: 27 July 2004 / Published online: 10 September 2004
Springer-Verlag 2004
Abstract Gold is an important by-product in many
porphyry-type deposits but the distribution and
chemistry of gold in such systems remains poorly
understood. Here we report the results of petrographic,
electron microprobe, laser ablation inductively coupled
plasma mass spectrometry (LA-ICP-MS), and otation
test studies of gold and associated copper suldes
within a paragenetic framework from the world-class
Batu Hijau (914 mt @ 0.53% Cu, 0.40 g/t Au) por-
phyry coppergold deposit, Indonesia. Unlike many
other porphyry coppergold deposits, early copper
minerals (bornitedigenitechalcocite) are well pre-
served at Batu Hijau and the chalcopyritepyrite
overprint is less developed. Hence, it provides an
excellent opportunity to study the entire gold para-
genesis of the porphyry system. In 105 polished thin
sections, 699 native gold grains were identied. Almost
all of the native gold grains occurred either within
quartz veins, attached to sulde, or as free gold along
quartz or silicate grain boundaries. The native gold
grains are dominantly round in shape and mostly 1
12 lm in size. The majority of gold was deposited
during the formation of early A veins and is domi-
nantly associated with bornite rather than chalcopyrite.
The petrographic and LA-ICP-MS study results indi-
cate that in bornite-rich ores gold mostly occurs within
copper sulde grains as invisible gold (i.e., within the
sulde structure) or as native gold grains. In chalco-
pyrite-rich ores gold mostly occurs as native gold
grains with lesser invisible gold. Petrographic obser-
Editorial handling: R. P. Richards
J. Arif T. Baker (&)
Economic Geology Research Unit, School of Earth Sciences,
James Cook University, Townsville, 4811, QLD, Australia
E-mail: Timothy.Baker@jcu.edu.au
Tel.: +61-7-47814772
J. Arif
Mine Geology Department, Batu Hijau Mine,
PT Newmont Nusa Tenggara, NTB Nusa Tenggara,
Lombok, Indonesia
vations also indicate a higher proportion of free
gold (native gold not attached to any sulde) in chal-
copyrite-rich ores compared to bornite rich ores. The
pattern of free gold distribution appears to correlate
with the otation test data, where the average gold
recovery value from chalcopyrite-rich ores is consis-
tently lower than bornite-rich ores. Our data suggest
that porphyry copper-gold deposits with chalcopyrite-
rich ores are more likely to have a higher proportion
of free gold and may require dierent ore processing
strategies.
Keywords Gold Porphyry Copper Batu Hijau,
Indonesia
Introduction
Gold-rich porphyry copper deposits (dened as those
with bulk Cu/Au atomic ratios of  <40,000; Kesler
et al. 2002) are among the largest reservoirs of gold in
the upper crust (Kerrich et al. 2000), and are one of the
largest revenue generators in the mining industry (Jones
1992). Several studies have addressed various aspects of
gold-rich porphyry deposits including experimental
work on phase and depositional relationships between
gold and copper-iron-suldes (e.g., Simon et al. 2000;
Jugo et al. 1998; Gammons and William-Jones 1997;
Cygan and Candela 1995), evaluation of the gold con-
tent of metal suldes and oxides (e.g., Kesler et al. 2002),
estimation of the gold and copper ratios and contents in
uid inclusions (e.g., Ulrich et al. 1999; Loucks and
Mavrogenes 1999) and conventional geological and pet-
rological studies that have noted the occurrence and
distribution of gold (see Kesler et al. 2002 for a com-
prehensive review). The review of gold-rich porphyry
copper deposits by Kesler et al. (2002) suggests that
gold commonly occurs in early potassic alteration
with bornite either as 5100 lm inclusions within or at
the edge of the sulde grains. Gold also occurs with
524
chalcopyrite in chalcopyrite-rich porphyry copper ores,
particularly where there is a later overprint by chalco-
pyrite-pyrite-bearing phyllic alteration. Kesler et al.
(2002) also showed that bornite contains one order of
magnitude more gold in solid solution than chalcopyrite
(1 ppm and <0.1 ppm, respectively); but state that this
does not adequately account for all the gold in porphyry
copper deposits and the gold is therefore likely present
as micron-scale native gold grains. Cuddy and Kesler
(1982) is one of the few published studies that have
evaluated the occurrences of gold both as native gold
grains and within suldes throughout the paragenesis of
gold-rich porphyry copper deposits. In this paper we
describe dierent gold occurrences throughout the
paragenesis of the world class Batu Hijau gold-rich
porphyry copper deposit (914 mt @ 0.53% Cu, 0.40 g/t
Au). This deposit has a well dened geological setting
(Garwin 2002), a well constrained vein and alteration
paragenesis (Mitchell et al. 1998; Clode et al. 1999;
Garwin 2002), and preserves abundant early copper
suldes (bornitechalcocitedigenitechalcopyrite) as
well as zones of later chalcopyritepyrite. We report the
results of petrographic, electron microprobe, laser
ablation inductively coupled plasma mass spectrometry
(LA-ICP-MS), and otation test studies of gold and
associated copper suldes within this context. The study
identies the diversity of gold occurrences within a single
porphyry copper deposit and highlights the importance
of understanding this variability for metallurgical pro-
cessing of dierent types of porphyry copper-gold
deposits.
Geological setting
Batu Hijau is an island arc-related porphyry copper
gold deposit located in the southwest corner of Sumb-
awa Island in the Sunda-Banda archipelago of Indonesia
(Fig. 1). Sumbawa lies along the tectonically active
Fig. 1 Map illustrating the
location of Batu Hijau and
occurrence of other major
porphyry CuAu deposits in
southeast Asia (modied from
Corbett and Leach 1998)
eastwest trending Sunda-Banda magmatic arc. The
island of Sumbawa comprises an Early Miocene to
Holocene volcanic arc constructed on approximately
1423 km of oceanic crust adjacent to the margin of the
Sunda continental shelf (Hamilton 1979; Barberi et al.
1987). Neogene calc-alkaline volcanic and sedimentary
rock sequences (volcaniclastic rocks, shallow marine
sedimentary rocks and limestones) form the basement of
Sumbawa, which is presently exposed in the southern
part of the island. Quaternary stratovolcanoes form the
northern part of Sumbawa and indicate a progressive
change from calc-alkaline to shoshinotic anities with
time (Garwin 2002). The Batu Hijau district is located
within an uplifted crustal block, within 30 km of a major
arc-transverse, left-lateral oblique-slip fault zone that
controls the distribution of Miocene volcanosedimenta-
ry units, the location of Neogene intrusions and the
present coastline of the island. The district features an
Early to Middle Miocene andesitic volcaniclastic rock
succession that dips gently in a westerly direction. This
rock sequence has been cut by several phases of Middle
to Late Miocene (5.93.7 Ma) intrusions (Garwin 2000).
These intrusions include hypabyssal andesites, equi-
granular quartz diorite plutons and late-stage tonalite to
granodiorite dikes, and are related to centers of por-
phyry-style mineralization.
The pre-ore rock units in the vicinity of the Batu
Hijau deposit consist of interbedded andesite tu breccia
and ner grained volcaniclastic sandstones and mud-
stones, which are intruded by porphyritic andesite and
two texturally distinct quartz diorite bodies (Clode et al.
1999). Multiple phases of tonalite porphyry were sub-
sequently emplaced into these rocks, and generated
hydrothermal alteration and copper and gold minerali-
zation in the deposit (Fig. 2). Three tonalite porphyry
stocks form the core of the Batu Hijau deposit and are
termed the Old Tonalite, Intermediate Tonalite, and
Young Tonalite (Clode et al. 1999). Garwin (2000),
using the U-Pb SHRIMP dating technique, showed that

Fig. 2 Lithology distribution on section 9080 N (modied after
Clode et al. 1999)
the emplacement of the tonalite porphyry intrusions was
rapid and that the three intrusions were emplaced within
90 ky (3.760.123.670.10 Ma).
Alteration and mineralization
Gold and copper grade are not uniform in the deposit
(Fig. 3a, b). In order to evaluate how sulde mineralogy
inuences the variation in copper-gold ratios (Fig. 4a)
block models of chalcopyrite, bornite and pyrite were
constructed (Fig. 4b, c, d). Mineralogical studies con-
ducted by Brosnahan (2002) have shown that the
abundance of copper sulde showed a good correlation
to sulfur and copper assays. Microprobe analysis indi-
cated that copper sulde in Batu Hijau is stoichiometric,
and hence the sulfur and copper ratios (S/Cu ratio) for
chalcocite, digenite, bornite, and chalcopyrite are
0.2522, 0.2803, 0.4036, and 1.0089, respectively. Theo-
retically, if the S/Cu grade ratio of the ore is >1.0089,
the sulde assemblage should consist of pyritechalco-
pyrite. This does not mean that bornite cannot be
present in relicts of non-overprinted rock, but if present,
they would have to be compensated for by a signicant
amount of pyrite. A S/Cu grade ratio <0.4036 should
indicate that most of the sulde assemblage is bornite
digenitechalcocite. If chalcopyrite or pyrite is present
a higher proportion of digenite or chalcocite should
also occur. The models show a contrast in distribution
525
between bornite and pyrite which are concentrated at the
top and the bottom of the deposit, respectively. The
presence of bornite and pyrite in the same sampling in-
terval (which is possible) will potentially yield the cal-
culated S/Cu ratio of chalcopyrite; therefore the
chalcopyrite model may not fully represent the dis-
tribution of chalcopyrite in the deposit. In the upper part
of the deposit the ratio of gold (g/t) to copper (%) is
approximately 1, but deeper in the deposit, the ratio of
gold to copper increases to 3 (Fig. 4a). This correlates
with a change from bornite>chalcopyrite mineralogy in
the upper part to chalcopyrite>bornite in the deeper
part (Fig. 4b and c). Furthermore, results from recent
deep drilling programs indicate that the sulde assem-
blages below the current ultimate pit boundary are
dominantly chalcopyrite and pyrite rather than bornite
(Fig. 4d).
Hypogene hydrothermal alteration, veins and sulde
mineralization developed in ve temporally and spa-
tially overlapping events termed Early, Transitional,
Late, Very Late and Zeolite alteration stages (Mitchell
et al. 1998). The early alteration consists of biotite
replacement of mac phenocrysts and groundmass, and
the development of magnetitebiotitequartz stringers
and EDM-like (early dark micaceous) biotitesericite
veinlets (cf. Meyer 1965). Secondary plagioclase occurs
along the selvages of early quartz veinlets. Early alter-
ation is pervasive within and proximal to the tonalite
porphyries, and although the fracture density and
alteration intensity rapidly decrease away from the
mineralizing intrusions, secondary biotite extends out-
ward for more than 500 m from the porphyry centre
526

Fig. 3 a Gold grade

distribution on section 9080 N
(modied after Clode et al.
1999). The area of the drill core
samples ( dashed ovals) is a
compilation of all sample
locations from other sections
(9020 N and 9120 N), projected
to section 9080 N. The gray
color in the center of the gold
shell is the Young Tonalite
body, which has weak gold
mineralization. b Copper grade
distribution in section 9080 N
(modied after Clode et al.
1999)

(Mitchell et al. 1998). Transitional alteration consists of
chlorite and vermiculite that replaced early-formed
biotite, and replaced oligoclasealbite by sericitecal-
cite. Magnetite is converted to hematite and/or chal-
copyrite (proximal) and pyrite (distal) (Mitchell et al.
1998; Clode et al. 1999). Late alteration consists of
feldspar replaced by sericite, and locally by andalusite
and pyrophyllitekaolinite, and the development of D
sulde veinlets and veins. The veinlets consist of pyrite
and quartzchalcopyrite locally with sphalerite and
tennantite. Very late hydrothermal alteration is also
characterized by feldspar destruction, but diers from
late alteration in that feldspar is replaced by smectite in
association with sericite and chlorite, and the sulde
minerals consist of sphalerite, galena, tennantite, pyrite,
chalcopyrite and locally bornite (Clode et al. 1999). The
last stage of hydrothermal alteration is recognized as
low temperature open space lling commonly along
vein centerlines and small open spaces in the wall rocks,
and consists of stilbitelaumontitecalcite (Mitchell
et al. 1998).
Copper and gold grades are positively correlated
with the density (volume percent) of quartz veins, with
early A veins comprising about 80% of the total vol-
ume of quartz veins and a similar proportion of the
copper (Mitchell et al. 1998). The A veinlets are thin
(less than 10 mm), wispy and discontinuous, and are
characterized by wavy to diuse wall-rock contacts
(Fig. 5a and b). The veins commonly contain feldspar,
magnetite, and abundant void space (up to 25%) that
probably reects original anhydrite subsequently lea-
ched during later hydrothermal and/or weathering
events. Hypogene suldes include chalcocite, digenite
and bornite, typically averaging 0.255 vol%. The
digenite typically occurs as exsolution lamellae within
bornite whereas chalcocite commonly occurs as a rim

Fig. 4 a Gold (g/t) and copper (%) grade ratio on section 9080 N.
The black line shows the outline of gold grade >1 g/t, whilst the
white line is the outline of ultimate open pit. The gold grade data
from below the ultimate pit is limited, but suggests that gold grade
is open at depth. Block models of b chalcopyrite, c bornite and
d pyrite distribution and abundance on section 9080 N based on
S/Cu ratios (see text for details)
surrounding the bornitedigenite grains suggesting the
chalcocite was deposited later (Fig. 5c). Generally, the
A veins are composed of granular quartz grains
<0.4 mm size in diameter, absent to weak banding
texture, no centerline and selvage alteration comprising
biotite and tan-colored feldspar (early alteration stage).
Quartz veins in transitional alteration are through-
going planar B and C veins. B veins are associated with
lower CuAu grades than A veins and have chalcopy-
ritebornite along vuggy centerlines and narrow oli-
gioclasealbite alteration envelopes (Fig. 5d). The
veins contain drusy quartz crystals around 1 mm in
diameter and commonly show banded texture and
white feldspar in selvage alteration. C veins are chal-
copyrite-rich with minor bornite and distinctive white,
feldspar-stable selvages consisting of variable mixtures
of albiteoligoclase and chloritesericite (Fig. 5e). The
D sulde veins are late stage and associated with feld-
spar destructive alteration of adjacent wall rocks
527
(Fig. 5b). The veins are generally 0.52 cm thick, con-
tain pyrite and quartz and have 2 to 10-cm-wide sericite
and smectite alteration selvages. These veins commonly
exploit pre-existing fracture zones and cut all lithologies
and earlier hydrothermal alteration.
There is also evidence to suggest that bornitedige-
nitechalcocite in early A veins was replaced by chal-
copyritepyrite when overprinted by later B, C and D
veins (e.g., Fig. 5f). The later suldation overprint in
Batu Hijau is irregularly distributed and its extent is not
fully known from current drilling. It appears to be
dominant in the deeper part of the deposit where
coexisting chalcopyrite and pyrite are more abundant
than bornite (Fig. 4b, c and d). This distribution is
unusual compared to other porphyry deposits where
bornite occurs either in the structurally deeper potassic
alteration zones that are outwardly overprinted by
chalcopyritepyrite mineralization associated with
phyllic alteration (e.g., Red Chris; Baker et al. 1997) or
where in some deposits bornite is rare and has been
mostly altered to chalcopyrite and pyrite (Kesler et al.
2002).
Limited uid inclusion results from Batu Hijau were
reported by Garwin (2000) on multi-solid halite-bearing
inclusions from B (to transitional A veins) and C veins.
Homogenization temperatures range from 450500 C
528
and are likely trapping temperatures based on the
coexistence with vapor-rich inclusions. Early A veins
were not sampled for the study but Garwin (2000) sug-
gested that these veins likely formed at >500700 C
based on the coexistence of magnetitebornitechal-
cocite (cf. Simon et al. 2000). The uid inclusion results
from B and C veins are also consistent with phase
equilibria temperature estimates based on the mineral-
ogy of the veins chalcopyritebornite (450500 C;
Simon et al 2000). Late D veins formed at temperatures
of <400 C (Garwin 2000).
Gold deportment and chemistry
Petrography
Samples were selected to represent the various vein
stages, mineralization assemblages, alteration styles,
grades and depth within the deposit. The upper portion
of the deposit is represented by samples from Bench 330
and 270, whilst the drill core samples represent the
middle to lower portion (sample location elevation
 529
b
Fig. 5 ab A veins (quartzbornitedigenitechalcocite) cut by a
D vein (chalcopyritepyrite) in a ne-grained volcanic rock,
strongly altered by biotite and feldspar (coin diameter is 2 cm).
The feldspars in the selvage of the D veins have been replaced by
sericite and smectite. The yellow box indicates the area of A veins
where D vein mineralization has replaced early suldes (bornite
digenitechalcocite) to chalcopyrite and pyrite. The light blue box
is where D vein mineralization weakly overprints A veins
(transition zone). Chalcopyrite content decreases away from the
D vein. The red box is where the A vein is unaected by D vein
mineralization overprint, thus bornitedigenitechalcocite are
preserved. c Digenite exsolution lamellar in bornite rimmed by
later chalcocite. d Two parallel B veins, with the centerline and
orthogonal fracture set inll of chalcopyrite and bornite. e B
(quartzchalcopyritebornite) and C (chalcopyritebornite) veins.
f Photomicrograph showing the rim of a bornite grain within an A
vein (from Fig. 5b) partially replaced by chalcopyrite

ranges from 330 m above sea level to 400 m below sea
level; Fig. 3a). The gold grades of the samples range
from 0.4 to 4.2 ppm. Polished thin section petrography
was carried out on 105 polished thin sections and 699
gold grains were identied (Table 1). Visible gold is lo-
cated in two sites: (1) gold grains in direct contact with
sulde, and (2) gold grains hosted by non-sulde min-
erals (quartz). The latter was classied as free gold
Fig. 7 Native gold grain sizes at Batu Hijau deposit. Mean value
excludes the outliers (>50 lm)
whereas the former had a wide variety of associated
sulde minerals (Fig. 6). From a total of 699 gold grains,
almost 65% are identied within or along grain
boundaries of bornitedigenite and bornite, approxi-

Table 1 Summary of gold deportment at Batu Hijau in relation to vein paragenesis

Quartz Common suldes Number of Number Mean size Ratio of free

vein type in quartz vein veins studied of gold grains of gold grains Au/Au in sulde
(microns)

A Bornite, digenite, chalcocite 75 556 6.9 0.23

B Bornite, chalcopyrite 54 123 7.8 0.41
C Chalcopyrite, pyrite 24 20 10.2 0.54
D Pyrite, chalcopyrite 21 0 N/a N/a

Fig. 6 Pie chart illustrating

native gold grain occurrences
and copper sulde association.
Native gold in Batu Hijau is
closely related to bornite and
the location of native gold
occurrence in the copper sulde
is equally distributed as
inclusions or along grain
boundaries of copper suldes
530
Fig. 8 a Native gold located in bornitedigenitechalcocite grains.
The digenite (chalcocite) exsolution commonly occur in a
roughly cubic or lamellar network within bornite. Observations
revealed all of the gold grains are actually located in the bornite
portion. b Native gold within bornite-only grains, with no
exsolution textures of digenite or chalcopyrite observed in the
grain. c Native gold located within chalcopyrite-only grains; minor
bornite is sometimes observed within the grains, but the native gold
is mainly surrounded by chalcopyrite. d A large free gold grain
between quartz grain boundaries. Sample numbers are in the top
right hand corner of each photograph
mately 14% occur within or along grain boundaries of
chalcopyrite, and 21% occur as free gold in quartz. The
occurrence of gold as inclusions within sulde and as
gold grains along sulde grain boundaries is almost
equal. Free gold becomes proportionally more abundant
in later vein stages (B and C; Table 1). LA-ICP-MS
identied a third category of gold occurring as solid
solution within sulde.
The occurrence and distribution of native gold in
Batu Hijau is closely related to quartz veins and their
paragenesis, whereby the early quartz veins (A veins)
contain almost 80% of total native gold observed and
the rest occurred in B veins and C veins respectively
(Table 1). Rare native gold in wall rock is located
<0.2 mm from the A veins. The gold grains mostly
range between 1 and 12 lm in diameter, but are
locally up to 97 lm (Fig. 7). The shapes of native gold
grains are dominantly well rounded to sub-rounded,
with a minor amount of angular to irregular shapes
(Fig. 8).
Chemistry of native gold
Native gold grain compositions were determined by
electron microprobe analysis. A total of 158 native gold
grains from 28 polished thin sections representing dif-
ferent paragenetic stages and locations in the deposit
were analyzed using an energy dispersive spectrometer
attached to electron probe microanalyzer (JEOL JXA-
84). The operating conditions included an accelerating
voltage of 20 kV and a beam current of 5nA. Calibra-
tion of the spectrometer was performed using gold, silver
and copper standards during each session. The optimum
diameter of microprobe analysis is approximately 3 lm,
thus the measurements were restricted to gold grains
that were larger than 4 lm, in order to avoid signal
contamination by other material surrounding the gold
grains. The measurements were made at least twice in
each selected spot (mostly in the center of the native gold
grain), using 40 s of counting time. The acceptable
measurement result falls in a range 2% from the
cumulative weight of 100%.
The results of microprobe analysis indicated that
most of the native gold contains signicant silver and
copper (Fig. 9). The ratios of gold, silver and copper

Fig. 9 Gold, silver and copper
composition of native gold
classied according to
associated mineralogy. The
precision of the microprobe
measurements (2r) for gold,
silver and copper are 4.4,
0.85, and 0.6%
respectively. Gold in copper
sulde has higher copper
contents than free gold, and
gold associated with
chalcopyrite mineralization
(both free and in contact with
chalcopyrite) has higher silver
contents
concentration vary, and are dependent on copper sulde
association and mineralization assemblages. Gold in
bornitedigenite and bornite (within A veins) contains
up to 8% copper (mean = 3.1%), signicantly more
than gold in chalcopyrite (within B and C veins; mean =
1.9%) and free gold (0.2%). The copper values are
interpreted to be real rather than contamination of the
signal by the host sulde due to careful selection of large
gold grains and because the results are consistent with
previous microprobe studies reported by Mitchell et al.
(1998) that noted up to 6% Cu. Silver contents are
highest in gold in chalcopyrite (mean = 10.9%) whereas
the silver content of gold in bornite has a mean average
of 4.0% and free gold has a mean average of 5.2%.
Thus, as the vein paragenesis evolved early bornite
contained gold with higher copper and lower silver
content (mean Cu/Ag = 1.2), and later chalcopyrite
contained gold with lower copper and higher silver
content (mean Cu/Ag = 0.2).
LA-ICP-MS analysis of gold in bornite, chalcopyrite,
and pyrite
Analytical setup
LA-ICP-MS analysis was used to determine the invisible
gold concentration of bornite in A veins ( n =17),
bornite in B veins ( n =15), chalcopyrite in B veins
531
(n =18), chalcopyrite in C and D veins ( n =18), and in
pyrite in D veins ( n =3). A total of 70 LA-ICP-MS
analyses were performed on 12 polished thin sections
from samples with grades >1 g/t Au. LA-ICP-MS was
carried out at the Geochemical Analysis Unit, ARC
National Key Centre GEMOC, Macquarie University.
The system used was a Merchantek LUV266 laser
microprobe connected to an Agilent 7500 s ICPMS.
Typical laser operating conditions included a repetition
rate of 4 or 5 Hz and an output power of 0.50.6 mJ/
pulse. These conditions produced a spot-size of 40
50 lm in sulde and an ablation rate of 1 lm/s.
Ablation was carried out in a mixture of He (0.250.3 L/
min) + Ar (1.11.15 L/min). The ICPMS was tuned to
give an oxide production <0.2% Th:ThO. Gas back-
grounds were collected for 60 s prior to ring the laser
and typical ablation times were 70100 s. Raw counts
were collected on the ICPMS in peak-hopping mode
(dwell time 30 ms) and displayed in time-resolved for-
mat. This allowed each ablation to be monitored to
identify heterogeneities due to uid or mineral inclu-
sions, and compositional variations with depth. Care
was taken to ensure that visible gold grains within sul-
de (particularly bornite) were not ablated during the
analysis and sulde grains that contained visible gold
were recorded (Table 2 and Fig. 10).
Quantication of trace element concentrations fol-
lowed the methods detailed in Norman et al. (1996).
Data reduction used the GLITTER software package
 532

Table 2 LA-ICP-MS results from bornite and chalcopyrite in dierent vein stages (A, B and C/D).< below detection limits

Sample Sulde/vein Au Au MDL Ag Ag MDL Sample Sulde/vein type Au Au MDL Ag Ag MDL

type (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

191-X-1 Bornite/A <1.980 1.980 142.710 3.060 193-3-6A Chalcopyrite/B <0.058 0.058 35.830 0.059
191-X-3 Bornite/A <2.210 2.210 151.540 3.560 193-3-6B Chalcopyrite/B <0.062 0.062 14.100 0.060
191-7-1 Bornite/A <2.010 2.010 157.600 3.180 1933-6C Chalcopyrite/B <0.064 0.064 12.480 0.066
6-2-1A Bornite/A <0.051 0.051 84.800 0.037 3A-2A Chalcopyrite/B <0.098 0.098 0.800 0.101
191-3-2 Bornite/A 0.186 0.032 125.750 0.026 3A-2C Chalcopyrite/B 0.081 0.074 10.960 0.109
6-2-2A Bornite/A 1.760 0.029 174.190 0.022 194-1-1A Chalcopyrite/B 0.050 0.010 8.340 0.008
6-2-3A Bornite/A <0.032 0.032 146.670 0.029 194-1-2B Chalcopyrite/B <0.021 0.021 7.030 0.013
191-8-2 Bornite/A 0.042 0.038 101.810 0.037 194-1-1D Chalcopyrite/B 0.258 0.013 14.210 0.010
6-2-1B Bornite/A <0.034 0.034 37.150 0.039 176-1 Chalcopyrite/B <0.012 0.012 12.300 0.009
142-2-6 Bornite/A 0.061 0.058 42.840 0.049 176-2 Chalcopyrite/B 0.132 0.008 14.310 0.006
142-10-1 a Bornite/A <0.039 0.039 251.230 0.027 176-3 Chalcopyrite/B <0.032 0.032 9.700 0.030
142-8-1 a Bornite/A <0.890 0.893 118.330 1.490 176-4 Chalcopyrite/B 0.088 0.016 15.540 0.027
142-1-1 a Bornite/A <1.740 1.740 101.920 3.110 3B-2-C Chalcopyrite/B <0.038 0.038 0.760 0.030
142-8-2 a Bornite/A <0.542 0.542 25.990 0.848 3B-2-D Chalcopyrite/B <0.034 0.034 0.950 0.027
142-1-4 a Bornite/A <2.060 2.060 151.520 2.890 3B-2-G Chalcopyrite/B <0.024 0.024 0.650 0.016
142-5-1 a Bornite/A <1.810 1.810 130.090 2.990 191-X-2 Chalcopyrite/B 0.129 0.014 2.159 0.011
142-1-2 a Bornite/A 0.970 0.045 339.950 0.048 6-2-4A Chalcopyrite/B 0.030 0.014 20.140 0.012
3A-2B Bornite/B 6.220 0.079 301.400 0.097 6-2-4B Chalcopyrite/B <0.044 0.044 15.120 0.031
3A-2D Bornite/B 7.990 0.054 314.940 0.058 49-1-2-1 Chalcopyrite/C/D 0.432 0.116 1.820 0.138
3A-2E Bornite/B 7.370 0.048 360.320 0.062 49-1-5 Chalcopyrite/C/D <0.090 0.090 6.110 0.104
194-1-1B Bornite/B 1.640 0.024 617.130 0.017 49-1-3 Chalcopyrite/C/D <0.139 0.139 1.200 0.174
194-1-1C Bornite/B 1.900 0.008 427.950 0.007 49-1-6A Chalcopyrite/C/D 0.132 0.124 3.110 0.159
3B-2-A Bornite/B 4.550 0.039 232.520 0.028 49-1-6B Chalcopyrite/C/D <0.028 0.028 3.720 0.040
3B-2-B Bornite/B 3.480 0.035 211.630 0.026 49-1-3-2 Chalcopyrite/C/D 0.307 0.143 5.610 0.169
3B-2-Eb Bornite/B 38.370 0.029 261.760 0.019 49-1-X Chalcopyrite/C/D <0.161 0.161 4.280 0.201
3B-2-F Bornite/B 3.630 0.031 269.380 0.026 193-1-2 Chalcopyrite/C/D <0.058 0.058 130.510 0.066
3B-2-H Bornite/B 7.090 0.015 205.480 0.009 193-1-3B Chalcopyrite/C/D <0.055 0.055 9.650 0.059
3A-1 a Bornite/B 3.130 0.060 255.990 0.079 193-3-4 Chalcopyrite/C/D <0.029 0.029 9.490 0.033
194-1-2Aa Bornite/B 2.850 0.050 549.740 0.040 193-3-5 Chalcopyrite/C/D <0.066 0.066 8.270 0.068
3B-1-Aa Bornite/B 1.350 0.030 199.620 0.024 193-3-8 Chalcopyrite/C/D <0.029 0.029 59.500 0.035
3B-1-Ba Bornite/B 0.537 0.034 192.740 0.025 194-13-1A Chalcopyrite/C/D <0.840 0.840 <1.36 1.360
3B-1-Ca Bornite/B 1.910 0.024 194.170 0.017 6-2-5A Chalcopyrite/C/D <0.041 0.041 8.500 0.031
6-2-6B Chalcopyrite/C/D <0.044 0.044 28.300 0.025
a
Bornite grains with visible gold grains
b
Gold grain ablated during analysis

Fig. 10 Histograms illustrating a the gold content and b the silver
content of bornite and chalcopyrite in A, B and C/D veins
measured by LA-ICP-MS. Only values above detection limits are
shown. Bornite consistently contains higher concentrations of gold
and silver than chalcopyrite
(Van Achterbergh et al. 2001; http://www.es.mq.edu.au/
gemoc/glitter). A combination of the NIST 610 glass
and a synthetic nickel sulde standard (PGE-A) was
used for the external standards, and Fe and S concen-
trations in the suldes were used as the internal standard
for the NIST and PGE-A respectively. The Cu, S and Fe
concentrations for bornite, chalcopyrite and pyrite were
assumed to be in stoichiometric proportions. An
uncertainty of 3% relative on the concentration of the
internal standard was incorporated into the error
propagation routines in GLITTER. The eect of this
uncertainty is to change absolute trace element abun-
dances but not relative abundances.
Results
Gold in bornite showed distinctly higher concentrations
compared to chalcopyrite (Table 2 and Fig. 10). Bornite
grains in A veins are typically smaller than bornite in B
veins, commonly <50 lm in diameter, and obtaining
clean ablation and sucient ablation volumes to achieve
low detection limits proved dicult. Therefore, results
from bornite in A veins are commonly below detection
533
Fig. 11 Summary of gold concentrations (above detection limits)
measured by LA-ICP-MS in bornite and chalcopyrite in dierent
vein stages compared with the SIMS results from Kesler et al.
(2002) that were carried out on Batu Hijau concentrates (therefore
not paragenetically constrained). The ranges from the SIMS results
were obtained from histograms plotted by Kesler et al. (2002),
however, the lower limits can only be estimated to <0.01 ppm
(also note that the detection limits vary for each analy-
sis; Table 2), however, gold values of up to 1.760 ppm
were detected (average = 0.600 for values above the
detection limit). Bornite grains in B veins were large
(>50 lm in diameter) and all grains contained signi-
cant gold ranging from 0.53738.370 ppm (Fig. 10a).
The latter is anomalously high and likely reects abla-
tion of a buried native gold grain. The average gold
content of the B vein bornite with this removed is
3.832 ppm (0.5377.990 ppm). Gold content of chalco-
pyrite in B veins was commonly below detection limits
and ranged from 0.0300.258 ppm for those values
above detection limits (average = 0.110 ppm; Fig. 10b).
Only three chalcopyrite grains contained gold above
detection in C and D veins (Table 2 and Fig. 10b).
Bornite also contained signicantly more silver than
chalcopyrite (Fig. 10); average content of silver in
bornite in A veins was 134.358 ppm (25.990
339.950 ppm), in bornite in B veins was 306.318 ppm
(192.740617.130 ppm), in chalcopyrite in B veins was
10.854 ppm (0.65035.830 ppm) and in chalcopyrite in C
and D veins was 18.762 ppm (1.200130.510 ppm).
Pyrite in D veins contained no detectable gold or silver.
Discussion
Kesler et al. (2002) used SIMS (ion probe) to measure
the gold content of chalcopyrite and bornite from con-
centrates at Batu Hijau (Fig. 11). LA-ICP-MS results
from this study show similar, although not identical,
results and conrm that bornite contains approximately
one order of magnitude more gold than chalcopyrite.
Experimental work by Simon et al. (2000) is also con-
sistent with this relationship with bornite accommodat-
534
ing approximately one order of magnitude more gold
than chalcopyrite. However, much higher concentra-
tions of gold occurred in bornite and chalcopyrite in the
experimental studies than those measured by Kesler
et al. (2002) and this study. Kesler et al. (2002) calcu-
lated that bornite and chalcopyrite saturated at 300
and 250 C at Batu Hijau respectively, and our results
are in broad agreement with their study. The saturation
temperatures are signicantly lower than the deposition
temperatures of bornite (500700 C) and chalcopyrite
(450500 C) at Batu Hijau (Garwin 2000) further sup-
porting Kesler et al.s (2002) suggestion that gold is ex-
solved during cooling of the deposit. They concluded
that the average gold grades of bulk ore and Cu/Au
ratios (40,000) could not be accounted for by the
invisible gold content of copper suldes alone and that
the exsolved gold must be account for the remainder. We
have shown that the additional gold in the deposit oc-
curs as small (112 lm), round native grains dominantly
associated with early bornite from which it was likely
exsolved. The high copper content of gold associated
with early bornite (Fig. 9) may also be used to support
the theory that gold was exsolved from bornite rather
than deposited directly from a hydrothermal uid.
Furthermore, later free gold (presumably precipitated
directly from a hydrothermal uid) has low to below
detection copper content.
Kesler et al. (2002) argued that the endowment of
gold in porphyry systems is likely xed by the amount of
gold that will enter copperiron suldes, and suggested
that the gold was subsequently exsolved as native grains
within or adjacent to the sulde and/or redistributed
during cooling or later alteration. We have shown that
approximately one fth of the native gold occurs as free
gold in quartz (Fig. 6). It is unclear as to whether the
free gold was deposited as an independent phase or
whether it was locally redistributed but its distinct
chemistry (copper-poor) suggests it was deposited as
an independent phase. In addition, the proportional
increase in free gold with later chalcopyritepyrite
dominant assemblages indicates that a signicant
amount was precipitated during cooling and later
alteration (Table 1). However, there is evidence to sug-
gest that some of the later chalcopyrite replaced earlier
borniterich mineralization, which may have resulted in
more native gold (and free gold?) because chalcopyrite
can not accommodate as much gold as solid solution in
its structure as bornite.
The observation that there is a higher amount of free
gold in the paragenetically later chalcopyrite-rich min-
eralization and lesser invisible gold is critical for pro-
cessing issues at Batu Hijau, and signicant for gold-rich
porphyry deposits in general. Modelling of S/Cu ratios
and drilling indicate that the deeper portions of the de-
posit are dominated by chalcopyrite and pyrite, and
there is an increase in Au/Cu ratios (Figs. 3 and 4).
Results of otation tests from 2002 and 2003 drilling
indicate that the average gold recovery from chalcopy-
ritepyrite ore is almost 5% lower than average bornite
chalcopyrite ore (Arif 2002; Dadang Prananta, pers.
comm. 2004) whereas copper recovery is consistent for
all types of sulde assemblages. We suggest that the low
gold recovery in the otation cells from chalcopyrite
pyrite assemblage ores relates to the decrease in invisible
gold and increase in free gold. This nding may have a
crucial impact concerning ore processing design at the
Batu Hijau deposit as the mine gets deeper in the future
and into the chalcopyritepyrite dominated ore. The
potential loss of gold may be rectied through installa-
tion of a gravity circuit to recover the free gold prior to
oatation. Installation of additional gravity circuits to
trap free gold has improved the gold recovery in several
signicant porphyry copper-gold deposits including
Alumbrera and Cadia (Keran et al. 1998; Dunne et al.
1999). Interestingly the gold-rich Alumbrera and Cadia
deposits both contain dominantly chalcopyrite-rich ores
(Ulrich and Heinrich 2001) suggesting that free gold is
more abundant in chalcopyrite dominant porphyry
systems than bornite-rich examples.
Acknowledgements PT Newmont Nusa Tenggara, an Indonesian
subsidiary of Newmont Mining Corporation, supported all of the
nancial expenses related to this study. We are grateful to Chris
Clode and Bruce Harlan, geology managers Batu Hijau, for mak-
ing the research project possible. Batu Hijau geologists are thanked
for their support and stimulating discussions. John Proett is
thanked for his insight into Au mineralization in porphyry
deposits. Thanks go to Norman Pearce at the Geochemical Anal-
ysis Unit, ARC National Key Centre GEMOC, Macquarie Uni-
versity for the LA-ICP-MS work. Reviews by Steve Kesler, Werner
Halter, Jeremy Richards and Larry Meinert signicantly improved
the manuscript.
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