2014 Society of Economic Geologists, Inc.

Economic Geology, v. 109, pp. 17051733

High-Sulfidation Epithermal Pyrite-Hosted Au (Ag-Cu) Ore Formation

by Condensed Magmatic Vapors on Sangihe Island, Indonesia*
Julia King,1, A.E. Williams-Jones,1 Vincent van
Jones2

Hinsberg,1 and Glyn Williams-

Department of Earth and Planetary Sciences, McGill University, 3450 University Street, Montral, Qubec, Canada H3A 0E8

1
2

Department of Earth Sciences, Simon Fraser University, 8888 University Drive, Burnaby, British Columbia, Canada V5A 1S6

Abstract
Although gold in high-sulfidation epithermal deposits generally occurs as the native metal or electrum, in
some deposits, a significant proportion of the gold is hosted in pyrite. Here we use a combination of petrography, whole-rock geochemistry, pyrite chemistry, crystallography, and phase stability relationships to
deter- mine how gold was transported and incorporated into pyrite in two relatively young high-sulfidation
epithermal deposits, where the gold occurs almost exclusively in solid solution or as nanoparticles in pyrite.
The genetically related Bawone and Binebase Au (Cu-Ag) deposits, located 1 km apart on the volcanic island
of Sangihe, northeastern Indonesia, are hosted by andesitic volcaniclastic rocks that were altered to a proximal
advanced argillic association of quartz + pyrite (py I) + pyrophyllite + natroalunite + alunite + dickite + kaolinite and a more distal intermediate argillic association of quartz + pyrite (py I) + kaolinite + dickite + illite. The
economic mineralization takes the form of multiple generations of auriferous pyrite, the first of which, pyrite
I (py I), developed during advanced argillic alteration. Mass balance calculations show that all elements were
mobile with the exception of Nb, Ti, some rare earth elements, and possibly Al.
The highest gold concentration is in pyrite II (py II), which occurs in veins that cut pyrite I. This drusy variety of pyrite is characterized by complex growth and sector zoning, and contains as much as 6.0 wt % Cu. The
elevated Cu concentrations correlate positively with Au and As concentrations, whereas the Ag concentration
correlates strongly with Au but not Cu. Later barite-enargite mineralization exploited py II veins and vugs, and
significant concentrations of Ag and Au are hosted by enargite, although the Au concentration in enargite is
lower than in py II or py I.
A model is presented in which the fluid responsible for advanced argillic and intermediate argillic alteration
and associated stage 1 gold mineralization was a condensed magmatic vapor derived from an oxidized magma.
The gold and other metals were transported as hydrated species that ascended through the volcanic pile via
fractures and zones of enhanced permeability to a depth between 900 and 1300 m, where the vapor condensed
at a temperature between 250 and 340C to form an acidic liquid with a pH of ~2.5; fO2 ranged up to four log
units above the hematite-magnetite buffer. Interaction of this liquid with the host andesites caused advanced
argillic and intermediate argillic alteration, including sulfidation of mafic minerals to form py I. During crystallization of py I, Au, Cu and Ag were adsorbed onto the surface of the pyrite and deposited as nanoparticles, or
were incorporated in the pyrite structure. Adsorption of Au, Cu, and Ag from the condensed vapor reached a
peak during the crystallization of vein-hosted py II, and the uptake of Ag and minor Au continued during later
crystallization of enargite. From the distribution of metals among growth and sector zones in py II, incorporation of gold and other metals appears to have been maximized when physicochemical conditions were relatively
stable. This is in contrast to the requirement for native gold precipitation, namely that physicochemical gradients be steep to ensure supersaturation of gold in the ore fluid.

Introduction
Although considerable progress has been made in understanding the formation of high-sulfidation epithermal precious metal deposits, opinion is still divided over the nature
of the ore fluid. There is general agreement that the characteristic residual (vuggy) silica and advanced argillic alteration are the result of interaction of rocks with the condensate
of highly acidic and oxidizing vapors (e.g., HCl, and H2S and
H2SO4 produced by reaction of H2O with SO2) from a proximal magma source (e.g., Hemley and Jones, 1964; Stoffregen
1987; Rye, 1993; Arribas 1995). However, until recently,
most researchers, noting that the ore minerals commonly fill
vugs and therefore postdate the alteration, have concluded
that the fluid responsible for the alteration did not transport
the ore
Corresponding author: e-mail, julia.j.king@gmail.com
*A digital supplement to this paper, containing four Appendices with raw
data, is available at http://economicgeology.org/ and at http://econgeol.geoscienceworld.org/.

0361-0128/14/4246/1705-29

metals (Stoffregen, 1987; White and Hedenquist, 1990; Arribas, 1995; Hedenquist et al., 1998). Instead, these researchers
have attributed the mineralization to collapse of the vapordominated system and transport of the metals by a magmatichydrothermal liquid with a large meteoric water component.
The discovery that gold mineralization in the Pascua deposit,
Chile, was contemporaneous with advanced argillic alteration
(Chouinard et al., 2005a), indicates that for some high-sulfidation epithermal deposits (cf. Voudouris, 2010) the two-stage
hydrothermal model does not apply. This, and a combination of fluid inclusion (Heinrich et al., 1999; Landtwing et
al., 2010) and experimental evidence (Archibald et al., 2001,
2002; Williams-Jones et al., 2002; Zezin et al., 2011b;
Migdisov and Williams-Jones, 2013; Hurtig and WilliamsJones, 2014) showing that gold, silver, and copper may be
considerably more
soluble in aqueous
vapors than
previously suspected, supports a model for these deposits
in which hydrothermal alteration
and economic
mineralization
were both
products of a magmatic
hydrothermal vapor (cf. Williams-Jones and

1705

Submitted: March 31, 2013

Accepted: December 9, 2013

1706
KING
Heinrich, 2005; Mavrogenes et al., 2010; Berger and Henley,
2011; Henley and Berger, 2011; Scher et al., 2013).
Most studies of high-sulfidation epithermal systems have
focused on deposits in which the gold occurs as a discrete
mineral or minerals (e.g., native gold, electrum, and/or a telluride phase, such as calaverite; Kesler et al., 1981; Stoffregen,
1987; Moritz et al., 2004; Deditius et al., 2008). However, in
some high-sulfidation deposits, notably the Pascua deposit in
Chile, a high proportion of the gold is hosted in sulfide
miner- als, particularly pyrite (e.g., Chouinard et al., 2005b;
Deditius et al., 2009). Here, we report results of a study of
two high- sulfidation epithermal deposits, Bawone (9.5 Mt
of ore with an average grade of 1.32 g/t Au and 3.97 g/t
Ag) and Bine- base (17.9 Mt of ore with an average grade of
0.76 g/t Au and
18.7 g/t Ag), located on Sangihe Island, Indonesia, in which
virtually all the hypogene gold is hosted in pyrite. Most
signifi- cantly, greater than 50% of this gold is in pyrite that
forms part of the early advanced argillic alteration mineral
association; the rest is contained mainly in pyrite veins that
cut the altered rocks. Thus, gold mineralization was both
contemporaneous with and postdated alteration. Based on
this and other obser- vations, we develop a model designed to
explain the genesis of the Bawone and Binebase deposits
involving transport of the metals in a highly acidic vapor and
sorption of the gold onto the surfaces of growing pyrite
crystals. Given the early tim- ing of the Au-Ag mineralization
and the observation that it is hosted almost exclusively by
pyrite, we also propose that these deposits are representatives
of a subclass of high-sulfidation epithermal precious metal
deposits, in which the bulk of the metal is hosted in pyrite
and the ore fluid was a condensed magmatic vapor.
Regional Geologic Setting
The Bawone and Binebase Au (Ag-Cu) deposits are located
in the southern part of Sangihe Island, the largest of the
islands in the 500 km long Sangihe arc, which runs northsouth from southern Mindanao, Philippines, to the north arm
of Sulawesi, and separates the Celebes and Molucca Seas
(Figs. 1, 2; Hall, 2000). The Sangihe arc formed as a result of
the westerly subduction of the Molucca Sea plate under the
Eurasian plate, whereas the facing Halmahera arc was produced by the easterly subduction of the Molucca Sea plate
under the Philippine Sea plate (Morrice et al., 1983; Morrice
and Gill, 1986; Garwin, 1990; Hall, 1996, 2000). Twenty-five
Quaternary stratovolcanoes are located along the length of the
arc; eight of these are active, including Awu at the northern
tip of Sangihe Island (Morrice and Gill, 1986; Fig. 1). Previous studies of volcanism along the Sangihe Arc have shown
that the arc is composed mainly of two-pyroxene and hornblende andesites. Calc-alkaline suites dominate and vary from
low to high K, depending on their distance from the volcanic
front (Morrice and Gill, 1986).
Sangihe Island has a lobate form defined by volcanic centers, the active stratovolcano, Awu, at the northern end and
the dormant/extinct stratovolcanoes, Tahuna and Kakiraeng,
and strongly weathered centers of Taware and Malisang to
the south (Fig. 1). The oldest part of the island is in the
southeast and the youngest in the northwest; new volcanoes
are forming off the northwestern tip and western shores of
Sangihe Island (Beaulieu, 2010). Given the heavy rainfall
(greater than 3 m

ET AL.

per year), dense vegetation and inferred rapid uplift due to

the compressive tectonic regime, even the oldest volcanoes, in
the southern part of the island where the Bawone and Binebase deposits are located, may be only tens of thousands of
years in age.
The southern part of Sangihe Island is dominated by clinopyroxene andesite flows, breccias, lahars, and tuffs of the
Tamako Group, except in the southern and eastern parts
where rocks of the Taware Group, Malisang Group, Binebase Group, and Pinterang Formation are exposed (Fig. 2).
The Binebase deposit is 1 km to the north of Bawone, and
both deposits are hosted by rocks of the Binebase Group. At
Bawone, the Binebase Group is overlain unconformably by
the Pinterang Formation, which covers the deposit, whereas
at Binebase, the deposit crops out and is strongly oxidized to
a maximum depth of 70 m (Fig. 3). The Binebase Group has
a northeasterly strike, moderate to steep southeasterly dip,
and comprises andesitic ash and crystal tuffs, hornblendepyrox- ene andesite flows, biotite-hornblende-magnetite
diorite and minor dacite to rhyolite flows, which are
interpreted to be volcanic and subvolcanic facies of the
extinct and eroded Taware volcano (Garwin, 1990). To the
east of the Binebase deposit, Binebase Group rocks are
overlain by rocks of the Tamako Group (consisting of
hornblende andesite flows, sills, and dikes), the proximal
facies of the dormant and/or extinct Kakiraeng volcano, and
to the south by the Pinterang For- mation. East of the
Bawone deposit, the Pinterang Forma- tion overlies the
Tamako Group rocks unconformably. This unit is thickest
(<100 m) in topographic lows, and consists of reworked
cross-bedded volcanic silts and sands, carbonates and
organic-rich sediments, which record a marine incursion in
the southeast part of Sangihe Island (Garwin, 1990). The
Pinterang Formation also contains slightly rounded, unoxidized aggregates of pyrite fragments, similar to pyrite II (py
II) from the Bawone and Binebase hypogene ores. The Pinterang Formation and Tamako Group overlie the Malisang
Group, which in turn unconformably overlies the Binebase
Group in the southeast part of the island. Stegodon fossils
found in conglomeritic channels in the Pinterang Formation indicate that the unit is between 2 million years and
60,000 years in age (de Vos et al., 2007). The Malisang Group
consists of hornblende andesite flows, sills, dikes, and diorite
intrusions that form local highs and is related to the Malisang
volcanic center (Garwin, 1990).
Local Geologic Setting
Recent oxidation has enriched both Au and Ag, and consequently, much of the potentially economic mineralization
of the Binebase deposit and a part of the Bawone deposit are
supergene in origin. However, both deposits have appreciable
reserves of hypogene sulfide mineralization. The inferred
resources, using a 0.25 g/t Au cutoff, are summarized in Table
1.
The Bawone and Binebase deposits are hosted by andesites
and dacites of the Binebase Group. The Binebase deposit is
exposed at the erosional surface and has been oxidized up to
a depth of 70 m (Fig. 3B). The host andesite is a crystal-rich
tuff containing 10 to 15 vol % of plagioclase laths and round
quartz crystals (12 mm in length and diameter, respectively) and occasional lapilli, and lithic fragments (0.53 cm

HIGH-SULFIDATION EPITHERMAL PYRITE-HOSTED Au ORE FORMATION, SANGIHE ISLAND, INDONESIA

1707

340'0"N

Sangihe I.

Awu (1327m)

Kakiraeng (1006m)

335'0"N

Binebase (65m)
Bawone (86m)

Malisang (295m)

325'0"N

330'0"N

Tahuna (697m)

320'0"N

Taware (306m)

10
Km
12540'0"E

12530'0"E

Fig. 1. Inset: Location of Sangihe Island. Digitial elevation model of Sangihe Island showing the locations and elevations
of the active volcano, Awu, dormant and/or extinct volcanic centers (Tahuna, Kakiraeng, Malisang) and the Bawone and
Bine- base deposits. Bathymetry contours are at 50-m intervals.

in diameter). Rare breccia zones containing a wide variety of

rock fragments are likely epiclastic deposits.
At Bawone, a thick andesite unit overlies flow-banded plagioclase-quartz-phyric dacite (Figs. 3A, 4A). In least-altered
Table 1. Inferred Resources for the Bawone and
Binebase Deposits (Stone, 2010)
Deposit

Tonnes

Au (g/t)

Ag (g/t)

Au (oz)

Ag (oz)

Oxide
Sulfide

3,475,000
5,999,000

1.66
1.12

9.16
0.97

185,464
216,020

205,933
187,089

Binebase Oxide
Sulfide

7,851,000
10,002,000

1.10
0.49

25.13
13.60

277,661
157, 573

6,343,299
4,373,443

Bawone

samples, the andesite contains 5 to 30 vol % white plagioclase laths (2 mm long) and rare, rounded quartz phenocrysts
(2 mm in diameter) in an aphanitic matrix. Conformable layers of welded crystal tuff are locally present in the andesite.
These contain 10 vol % of megascopic crystals of <3-mm-long
plagioclase laths and rare, rounded <3-mm-diameter quartz
grains. This unit is intruded by hypabyssal andesitic porphyry (Fig. 3A). The hypabyssal porphyry contains 20 vol %,
5 mm long, subhedral to euhedral hornblende, magnetite,
biotite and plagioclase phenocrysts, and rare quartz eyes in
an aphanitic matrix. An intrusive breccia with subangular
to subrounded, 1- to 10-cm-diameter fragments of the host
andesite and dacite generally defines the margins of the hyp-

HIGH-SU

KING ET AL.
12535'0"E

12540'0"E

Extinct Volcano
Intrusions
330'0"N

330'0"N

Quaternary Alluvium
Pinterang Formation
Tamako Group

Binebase (65 m)

Batunderang Group
Malisang Group

Bawone (86 m)

Binebase Group
Taware Group

Malisang (295 m)

Taware (306 m)

325'0"N

325'0"N

1708

4
Km

12540'0"E

12535'0"E

Fig. 2. The geology of south Sangihe Island and the location of the Bawone and Binebase deposits, modified from Garwin
(1990).
Soil
Pinterang Formation
Oxide zone

A
BID63

Binebase Group
Andesitic crystal tuff

BID27 BID72

BID11

BOD42

BOD3

BID69

BID16
BID56

BID15

BOD1

BID57

Soil
BID60
BID66

Pinterang Formation
Oxide zone/weathered
Binebase Group
Porphyritic Intrusion
Binebase Group
Andesite porphyry
Andesitic tuff
Dacite

100 m
25 m
100 m

25 m

Fig. 3. Representative lithological cross sections (A) through the Binebase deposit (NW-SE) and (B) through the Bawone
deposit (SW-NE) based on drill holes. The black lines show the locations of the drill holes. Most primary features have been
destroyed in the oxide zone but the original nature of the rock is assumed to have been the same as that of the underlying
bedrock.

LFIDATION EPITHERMAL PYRITE-HOSTED Au ORE FORMATION, SANGIHE ISLAND, INDONESIA

1709

B
Mag

Pl

Bt
Hbl

C
D

Kao + Qtz + Al

Py I
Py I + Qtz
Py II

Fig. 4. Photographs of the host rocks of the Bawone and Binebase deposits (cut slabs and core). (A) Argillically altered
flow-banded dacite, the basal unit of the Binebase Group at Bawone, showing phenocrysts and a matrix replaced by kaolinite
and quartz. (B) Plagioclase (Pl)-biotite (Bt), hornblende (Hbl)-magnetite (Mag) andesite porphyry. (C) Vein of py II (brassy)
with fragments of py I (black) in a matrix of vuggy py I with py II occasionally lining vugs. (D) Advanced argillic (alunite =
Al, pyrite = Py, quartz = Qtz) alteration of fragments (light gray) in a matrix of fine-grained quartz and pyrite (dark gray).
The scale bar is 1 cm.

Pinterang Formation (poorly consolidated volcaniclastic sandstones and siltstones, organic-rich siltstones, and calcareous
mudstones) ranges up to 100 m thick and is separated from
the Binebase Group rocks by a thin (several-cm) oxide layer,
possibly a paleosol. The Pinterang Formation is overlain by
an oxidized soil that is up to 4 m thick.
Hydrothermal Alteration
In hand sample, the altered rocks vary from dark gray to
white in color, depending on the pyrite content, and from very
hard (quartz dominated; Fig. 4C) to powdery (clay dominated;
Fig. 4D) in drill core; the latter variation commonly occurs
over intervals of tens of centimeters to tens of meters. Alteration intensity is variable. In some samples, the primary minerals have been completely replaced by secondary minerals,
destroying all primary textures, whereas in other samples, volcanic textures are preserved (Figs. 4D, 5A). The pervasively
altered samples comprise very fine-grained, clay particles
intergrown with fine-grained, generally anhedral, equigranular quartz and pyrite (Fig. 5A, B, D). Less intensely altered

samples commonly retain porphyritic textures, although the

phenocrysts have generally been replaced by kaolinite or
dickite. The most intensely altered samples consist of a finegrained mosaic of intergrown anhedral quartz, clay minerals
(kaolinite, dickite, pyrophyllite), sulfate minerals (alunite,
natroalunite) and pyrite. Hereafter, the fine-grained, anhedral pyrite intergrown with clay minerals and quartz will be
referred to as pyrite I (py I).
Alteration created secondary porosity in the form of mmscale vugs (formed by the dissolution of phenocrysts) and
irregular, cm-scale cavities. The latter are commonly infilled
by alunite, and/or pyrophyllite, and/or drusy pyrite, and/or
chalcocite, and/or barite crystals (Figs. 4C, 5C, D).
Alteration is most intense (few primary textures preserved)
along subvertical fluid conduits that fan out horizontally at
lithologic contacts (Fig. 6A). Distal to the mineralized zones,
alteration is generally less intense, primary volcanic textures
and minerals are preserved, and the rock is more competent.
The matrix of the rock is preferentially altered and has a grey
to light-brown color.

Qtz

Py I
Al

Py I

D
Py II

Py II

Cc
Brt

Py I + Qtz

F
Py II

Sp

El

Ccp

Apy
En

Brt
Brt

Fig. 5. Photomicrographs showing the textures of the altered and mineralized rocks in reflected light (10 m scale bar).
(A) Amphibole phenocrysts replaced by py I in a groundmass replaced by fine-grained quartz, py I, kaolinite dickite.
(B) Fine-grained association of quartz, alunite and py I, typical of argillic alteration. (C) Massive py II and a vug containing
rare chalcocite (Cc) and barite (Brt) crystals. (D) Growth zoned drusy crystals of py II infilling a vug in andesite altered to
fine-grained py I and quartz (blue-grey is epoxy). (E) Fractured and zoned crystals of massive py II cut by a barite-enargite
(En) vein. (F) Sphalerite (Sp), arsenopyrite (Apy), chalcopyrite (Ccp) and electrum (El) crystals in a coarse-grained barite
matrix. The earliest stage of gold-silver mineralization is manifest by fine-grained py I associated with equally fine-grained
quartz and clay minerals (A, B). This was followed by a second generation of Au-Ag mineralization in the form of coarsegrained py II (C, D, E). The third generation of Au-Ag mineralization is represented by barite-enargite (En) veins that commonly contain brecciated py II crystals (E). Rare cm-scale veins of barite containing electrum, sphalerite, arsenopyrite and
chalcopyrite that cut py I and py II mineralization constitute a fourth generation of Au-Ag mineralization observed only in
the Binebase deposit.

1711

1711

HIGH-SULFIDATION EPITHERMAL PYRITE-HOSTED

KING ETAu
AL.
ORE FORMATION, SANGIHE ISLAND, INDONESIA
Supergene zone
IA I (qtz + py + kao dck)
IA II (qtz + ill py)

A
BID 27
BID 63
BID 16

BID 15

BID 11

BID 72
BID 69
BID 56

BID 57

Overburden and
Pinterang Fm.
AA I (qtz+py+prlnal)
AA II (qtz+pynaldckkao)
BOD 1
AA III (qtz+py+kaoal)
IA I (qtz+kaopy)

BOD 42

BOD 3

BID 60
BID 66

100 m

25 m
100 m

25 m

Fig. 6. Representative cross section (A) NW-SE through the Binebase (BID) deposit and (B) SW-NE through the
Bawone (BOD) deposit showing the distribution of hypogene alteration facies established using X-ray diffraction analysis and
core log- ging. The locations of drill holes are indicated by the black lines. Abbreviations: alunite = al, dickite = dck, illite =
ill, kaolinite
= kao, natroalunite = nal, pyrite = py, pyrophyllite = prl, quartz = qtz.

Two main alteration facies have been recognized, advanced

argillic and intermediate argillic, based on the mineral associations of quartz + pyrite + pyrophyllite + natroalunite +
alunite + dickite + kaolinite and quartz + pyrite + kaolinite
+ dickite + illite, respectively. Quartz and pyrite are nearly
ubiquitous alteration phases, but the proportions of these
minerals and those of the accompanying phases, which were
used to define the alteration facies, vary significantly. In principle, the advanced argillic and intermediate argillic facies
can be subdivided into subfacies with fewer minerals that
reflect different physicochemical conditions. For example,
at quartz saturation (the case here), pyrophyllite is stable
at higher temperature than dickite, and dickite is stable at
higher temperature than kaolinite (Hemley et al., 1969; Stoffregen and Alpers, 1987; Stoffregen and Cygan, 1990). Similarly, natroalunite is stable at higher temperature than alunite
provided that the K/Na ratio of the fluid is relatively constant (Stoffregen and Cygan, 1990). Finally, illite is stable at
higher pH than kaolinite, dickite, and pyrophyllite. In view of
these relationships, mapping, X-ray diffraction and infrared
spectroscopy (TerraSpec) evidence were used to subdivide
the advanced argillic association into a high temperature,
lower pH subfacies (advanced argillic I) of quartz + pyrite
+ pyrophyllite natroalunite, an intermediate temperature,
low pH, subfacies (advanced argillic II) of quartz + pyrite
natroalunite dickite kaolinite, and a low temperature,
low pH subfacies (advanced argillic III) of quartz + pyrite +
kaolinite + alunite (see Discussion; Temperature and pH) .
The intermediate argillic association was subdivided into a
low pH subfacies (intermediate argillic I) of quartz + kaolinite pyrite dickite and a higher pH subfacies of quartz +
illite pyrite (intermediate argillic II).
The alteration facies are zoned, both vertically and horizontally, and the intensity of alteration decreases with depth and

laterally away from apparent fluid conduits. At Bawone, the

upper part of the deposit is dominated by advanced argillic
alteration. However, at Binebase the upper part of the deposit
is intensely oxidized due to weathering and supergene processes, and advanced argillic alteration is not observed (Fig.
6B). The Bawone deposit was protected from the effects of
weathering by the overlying Pinterang Formation (Figs. 3A,
6A). Advanced argillic alteration in the Bawone deposit terminates abruptly at the contact with the overlying Pinterang
Formation, although a thin (cm-scale) oxide layer is present
at this contact. This layer indicates that the uppermost part
of the deposit was previously oxidized, and perhaps partially
removed by erosion, prior to deposition of the Pinterang
Formation.
Advanced argillic alteration at Bawone forms subhorizontal zones just below the Pinterang Formation and about 75 m
lower stratigraphically, at the contact with a zone of andesitic
tuff (Figs. 3A, 6A). Both zones appear to flare outward from
a steeply inclined advanced argillic alteration zone that likely
represents the conduit for the altering fluids. The upper parts
of the subhorizontal alteration zones and the central part of
the inclined alteration zone are dominated by the high temperature, advanced argillic I alteration subfacies. Below the
subhorizontal advanced argillic I alteration zones and adjacent
to the inclined advanced argillic I alteration zone, this subfacies changes to advanced argillic II alteration and distally to
intermediate argillic I alteration. Low temperature advanced
argillic III alteration is present only at depth and locally may
develop directly below advanced argillic I alteration without
intervening advanced argillic II alteration (Fig. 6A). Given its
distribution, the advanced argillic III alteration may be related
to the unmineralized hypabyssal porphyry intrusion (Fig. 3A).
At Binebase, the zone of supergene oxidation passes directly
into intermediate argillic alteration. The latter comprises a

blanket of intermediate argillic I alteration with several subvertical roots that pass downward and laterally into intermediate argillic II alteration (Fig. 6B).
Hypogene Mineralization
Neither free gold nor electrum is observed in the hypogene zone of the Bawone deposit and very rarely in the Binebase deposit. Instead, the hypogene gold in both deposits is
invisible, i.e., hosted almost exclusively by pyrite. Silver is
also invisible, hosted by both pyrite and enargite, and copper occurs mainly in pyrite and enargite (volumetrically much
less abundant than pyrite), as well as rare grains of chalcocite
in vugs (Fig. 5C). Gold (-silver) mineralization occurred in
three stages: (1) an early stage of disseminated Au-Agbearing pyrite during advanced argillic and intermediate argillic
(minor) alteration (pyrite I; Figs. 5A, B, D, 7B), (2) an intermediate stage characterized by multiple generations of lenses,
veins and breccias containing subhedral to euhedral, drusy,
and massive to semimassive Au-Ag-Cu-bearing pyrite II (py
II; Figs. 5C-E, 7A, C), and (3) late-stage barite-enargitepyrite II veins (Figs. 5C, E, 7C). At Binebase, there is a fourth

stage in the form of rare barite, base-metal sulfide, and electrum veins (Figs. 5F, 7D).
The earliest gold occurs in py I, which is an ubiquitous
alteration product intergrown with quartz and hydrous alumina-rich phases and occurs as small (230 m diameter),
isotropic, anhedral grains, accounting for 2 to 20 vol % of the
rock; the gold grade corresponds to the proportion of pyrite
in the rock. As part of the advanced argillic alteration and to
a much lesser extent the intermediate argillic alteration, this
stage of mineralization was focused along vertical structures
and spread out laterally near the top of the deposit where
fluids were confined by less-permeable strata or paleo-water
tables. At the Bawone deposit, advanced argillic I alteration is
also concentrated in a subhorizontal zone below an impermeable andesitic tuff about 75 m below the base of the Pinterang
formation (Figs. 3A, 6A).
The second stage of gold mineralization is characterized
by veins, veinlets, blebs, breccias, lenses, and massive bodies
of coarse-grained, brassy py II, which overprinted advanced
argillic alteration and intermediate argillic I alteration,
exploited the secondary porosity created during alteration,

Qtz + Al
Py II

Py I
Brt

D
Brt
Py II

En

Brt
Ccp

El

Fig. 7. BSE images of auriferous pyrite, py I and py II, and later generations of mineralization. The scale bar is 100 m
unless otherwise indicated. (A) Fragment of drusy py II exhibiting strong growth zoning in a barite (Brt) vein. (B) Disseminated PyI in a matrix of quartz (Qtz) and alunite (Al). (C) Barite-enargite (En) vein with m-scale, homogeneous subhedraleuhedral enargite crystals intergrown with mm-scale subhedral barite surrounding fragments of py II. (D) Electrum (El)
grain surrounded by subhedral chalcopyrite (Ccp), barite (Brt), and sphalerite (Sp) (10 m scale bar).

earlier py II veins, as they are commonly lined by fractured

py II crystals, and py II commonly occurs as brecciated fragments in the veins, indicating that they were incorporated
mechanically during barite-enargite vein formation (Figs. 5E,
7C). In the centers of these veins, intact, blue-purple, isotropic subhedral to euhedral (1060 m long) rectangular or
bladed enargite crystals and fractured py II fragments are suspended in a matrix of coarse-grained, subhedral to drusy barite crystals. Texturally, the enargite is homogeneous,
unzoned, and appears to have coprecipitated with barite
(Figs. 5E, 7C). Barite and enargite also commonly occur in
vugs. The den- sity of barite-enargite veins (the proportion of
veins relative to host-rock) is variable but generally correlates
with that of py II veins, suggesting that both vein stages
exploited the same structures.
Although electrum is volumetrically insignificant, the gold
grade of these rare base-metal sulfide-electrum-barite veins is
20 times higher than that of the auriferous-pyrite dominated
zones of the deposit. In the Binebase deposit, these veins
range from 0.5 to 8 cm in width and are observed in the center
of the hypogene mineralization. This rare vein association was
only observed at Binebase, where it crosscuts all other mineralization stages, except for the enargite-barite veins. The
relative timing of these two late vein generations therefore
cannot be established. Mineralogically, the base metal sulfideelectrum-barite veins comprise small subhedral to euhedral
crystals of spalerite, arsenopyrite, chalcopyrite, galena, pyrite,
electrum and Sb-sulfides that occur as aggregates in a coarsegrained matrix of euhedral barite crystals (Figs. 5F, 7D).
Distribution of gold-silver mineralization
Gold and silver grades in the Bawone deposit are highest
just below the contact with the Pinterang Formation, decrease
with depth and then increase again just below a thin tuffaceous andesite unit in a zone of advanced argillic I alteration
(Figs. 3A, 6A, 8). Metal concentrations correlate with the proportion of py II, pyrite breccias and/or barite-enargite veins. A
similar geometry is inferred for the hypogene mineralization
at Binebase. However, because the upper part of the Binebase deposit was subjected to supergene oxidation, we infer

Au

Ag Cu

As

Sb

40
Depth (m)

and crosscut fine-grained py I. As is the case with py I, the

gold grade is controlled by the abundance of py II, which
to
90 vol
forms
3 % of the rock, although py II is variably enriched
in gold. In thin section, py II is coarse grained (0.12 mm
long), massive or net-textured, and ranges in morphology
from anhedral to euhedral (Figs. 5A, D, 7A, C). Botryoidal
and drusy textures also are common, and many crystals are
complexly zoned (Fig. 7A). In reflected light, some pyrite II
crystals have an anhedral blue anisotropic core, which chemically is indistinguishable from the rest of the crystal (Fig. 5E).
Rare, isolated anhedral chalcocite crystals (3 mm in diameter)
are observed locally in vugs rimmed by drusy py II (Fig. 5C).
Growth zoning of py II crystals on the m-scale is common,
particularly in drusy crystals, which show a relatively stable
growth history recorded by continuous growth surfaces. It is
also observed in massive pyrite composed of crystals that grew
separately and were later annealed, resorbed, brecciated and
overgrown (Fig. 7A).
Pyrite I and II are commonly crosscut by barite-enargite
veins (0.25 cm wide). These veins appear to have re-opened

60

80

3000
20
10

20
0

2000

50
00

10
00

250
50

Concentration (ppm)

Fig. 8. The concentrations of Au, Ag, Cu, As, and Sb (ppm) in a drill hole
from the Bawone deposit (BOD1); Pb and Zn concentrations were below the
detection limit and Mo and Ba were not analyzed.

that any high-grade hypogene mineralization in this deposit

was at the level of the supergene zone. This interpretation is
consistent with the observation that the remaining hypogene
mineralization has a much lower concentration of gold and
silver than the Bawone deposit (Table 1).
Assay data for 1m intervals of drill core for Bawone and
Binebase, made available by East Asia Minerals Corp., show
that there is a strong spatial correlation between Au and Ag
concentrations, and also of As with Cu, and a weaker correlation of Cu and As with Sb (and Pb and Zn, not shown) concentrations (Fig. 8). Molybdenum concentrations are below the
2 ppm detection limit. The distribution of Au, Ag, As, and Cu
is vertically zoned, with the highest concentrations of these
elements occurring at the top of the hypogene zone. The
highest Au value coincides with high Cu, As, and Sb values
reflecting the presence of barite-enargite veins. This relationship, however, does not hold for the second highest Au value
(Fig. 8). Indeed, most of the higher Cu, As, and Sb values are
accompanied by only minor to negligible enrichment in Au.
We interpret these metal distributions to indicate that bariteenargite veins contributed only minor amounts of gold and
locally re-opened veins of py II to produce the coincident Au,
Cu, As, and Sb peaks.
Mass Changes During Alteration
Fifty-four drill core samples of the different lithological
units and alteration types were analyzed for major, trace, and
rare earth elements (REE) by inductively coupled plasmamass spectrometry (ICP-MS), and for gold by instrumental
neutron activation analysis (INAA), by Actlabs in Vancouver
(Table 2). The compositions of the altered rocks were compared to those of the least-altered rocks to evaluate the gains
and losses of elements during alteration. In order to assess
these mass changes, it was first necessary to identify potentially immobile elements that could be used to normalize

Table 2. Major Element Compositions from Drill Core and Hand

d.l.
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
Total
LOI

IA I
BOD1-134.5

IA I
BOD3-158.8

IA I
BOD3-85.4

IA I
BOD3-74.1

IA I
BOD3-106.4

IA I
BOD3-83.3

IA I/BaEn
BOD3-99.2

IA I/BaEn
BOD3-96.8

(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)

0.01
0.001
0.01
0.01
0.001
0.01
0.01
0.01
0.01
0.01
0.01

55.4
0.546
19.8
4.26
0.008
0.75
0.78
0.35
2.17
0.1
98.53
14.36

64.68
0.547
14.36
8.38
0.009
0.02
0.03
0.05
0.08
0.08
100.1
11.82

8.2
0.036
0.33
35.08
0.005
0.02
0.04
0.06
0.02
b.d.
66.75
23.02

58.66
0.528
9.13
13.45
0.006
0.01
0.06
0.56
0.69
0.06
99.83
16.69

51.41
0.484
2.91
27.98
0.007
0.02
0.05
0.06
0.02
0.04
100.3
17.33

48.19
0.541
2.85
30.09
0.006
0.02
0.04
0.07
0.04
0.05
100.3
18.38

19.69
0.185
0.3
40.04
0.006
0.02
0.03
0.04
0.05
b.d.
82.61
22.25

85.78
0.501
2.34
6.14
0.006
0.02
0.06
0.04
0.04
0.08
99.49
4.49

La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Y
Yb
Lu

(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)

0.05
0.05
0.01
0.05
0.01
0.005
0.01
0.01
0.01
0.01
0.01
0.005
0.5
0.01
0.002

15.8
32.1
3.83
14
2.66
0.791
2.18
0.36
2.19
0.45
1.41
0.237
12.8
1.78
0.31

8.91
16.5
1.94
8
1.64
0.596
1.2
0.14
0.72
0.15
0.52
0.103
4
0.72
0.119

11
7.29
0.49
1.21
0.34
b.d.
1.51
0.04
0.09
0.02
0.09
0.014
1.3
0.08
0.012

5.52
8.67
0.96
3.95
0.81
0.197
0.61
0.13
0.76
0.19
0.75
0.157
5.6
1.02
0.173

5.38
8.77
1.17
4.15
0.78
0.155
0.57
0.08
0.42
0.09
0.43
0.08
3
0.61
0.101

6.03
10
1.33
4.67
0.84
0.185
0.58
0.09
0.44
0.08
0.39
0.067
2.8
0.52
0.091

8.38
8.03
0.79
2.55
0.61
0.472
1.02
0.1
0.28
0.07
0.23
0.042
2.5
0.31
0.053

13.9
26
2.97
12.1
2.31
0.649
1.49
0.16
0.89
0.16
0.73
0.146
5.2
1.03
0.174

Ag
As
Au
Ba

(ppm)
(ppm)
(ppb)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)

Bi
Co
Cr
Cs
Cu
Ga
Ge
Hf
In
Mo
Nb
Ni
Pb
Rb
Sb
Sc
Sn
Sr
Ta
Th
Tl
U
V
W
Zn
Zr

0.5
5
2
3
0.1
1
20
0.1
10
1
0.5
0.1
0.1
2
0.2
20
5
1
0.2
1
1
2
0.01
0.05
0.05
0.01
5
0.5
30
1

b.d.
487
b.d.
327
b.d.
13
b.d.
0.5
40
18
1.8
2.2
b.d.
b.d.
6.4
b.d.
8
36
b.d.
11
b.d.
248
0.35
2.79
2.28
1.02
128
b.d.
1,060
81

0.5
64
306
129
8.4
10
b.d.
b.d.
170
28
2.8
1.8
b.d.
5
2.2
b.d.
49
b.d.
2.8
13
b.d.
702
0.18
1.53
1.34
0.59
158
4.1
140
78

11.5
1,350
1,500
178,900
26.7
47
b.d.
0.2
4,550
4
0.6
0.2
0.4
28
1.1
b.d.
174
b.d.
112
b.d.
15
1,484
0.06
0.5
4.56
0.14
8
19.2
b.d.
6

b.d.
124
751
6,822
0.6
23
b.d.
b.d.
1,780
7
b.d.
2.4
b.d.
4
2.7
b.d.
12
1
10
9
b.d.
477
0.18
1.51
0.68
0.47
80
4
1,030
86

0.8
66
1,110
3,050
1
108
30
0.2
490
10
b.d.
2
b.d.
12
2.6
30
38
3
2.5
7
1
298
0.2
1.19
1.31
0.87
46
4.4
360
75

0.7
22
1,190
4,094
1.4
112
30
b.d.
2,590
7
b.d.
1.6
b.d.
6
2.7
30
25
b.d.
b.d.
5
b.d.
310
0.15
1.96
0.48
0.55
39
9.9
100
58

3.9
1,180
2,000
98,830
3.6
104
60
0.3
4,540
3
0.5
0.8
0.2
14
1.3
40
57
2
70.5
3
5
772
0.08
0.5
0.16
0.38
11
2.6
b.d.
30

b.d.
19
723
212
5
18
b.d.
b.d.
270
8
1.2
3.1
0.1
13
2.3
b.d.
18
b.d.
4.8
10
b.d.
515
0.21
2.05
0.36
1.68
33
6.4
320
144

Samples from the Bawone (BOD) and Binebase (BID) Deposits

Porphyry
AA I
BOD3-49.8

AA I
BOD3-55

AA I
BOD3-85.5

56.29
0.53
13.22
8.23
0.009
0.01
0.08
0.76
1.35
0.12
99.58
18.98

43.28
0.373
6.17
15.17
0.01
0.01
0.05
0.42
0.47
0.04
84.1
18.11

42.65
0.492
3.28
32.38
0.007
0.02
0.04
0.15
0.15
0.04
99.82
20.61

8.79
16.3
1.92
7.94
1.49
0.442
1.13
0.18
1.04
0.25
0.86
0.174
6.6
1.16
0.189

9.01
14.8
1.96
7.17
1.56
0.349
1.55
0.16
0.69
0.15
0.56
0.101
5.2
0.78
0.13

4.95
8.42
1.14
3.91
0.75
0.176
0.53
0.07
0.39
0.08
0.35
0.065
2.5
0.45
0.085

b.d.
38
166
779
b.d.
10
20
b.d.

AA I
BOD3-48.6

AA I
BOD3-100

AA I
BOD3-78.7

48.8
0.492
10.38
17.76
0.007
b.d.
0.06
0.48
0.71
0.1
99.86
21.06

29.11
0.377
0.26
46.64
0.009
0.02
0.04
0.05
0.03
0.02
100.1
23.58

8.74
0.22
1.25
59.44
0.014
0.03
0.05
0.06
0.02
0.02
100.8
31.01

63.84
0.43
7.59
10.06
0.005
0.01
0.06
0.84
0.81
0.08
99.15
15.42

49.79
0.46
10.59
16.73
0.01
0.02
0.06
0.38
0.36
0.12
97.66
19.13

51.37
0.474
11.21
12.06
0.003
b.d.
0.07
0.92
1.21
0.08
97.92
20.52

53.65
0.603
12.29
12.72
0.008
0.02
0.12
0.71
0.71
0.2
100
19

20.65
0.684
19.21
30.85
0.012
0.03
0.07
0.17
0.18
0.22
99.21
27.12

7.79
14
1.62
6.71
1.36
0.377
0.98
0.16
0.82
0.19
0.73
0.148
5.5
1.04
0.177

2.93
4.48
0.57
2
0.37
0.086
0.27
0.04
0.26
0.08
0.3
0.057
2.1
0.46
0.075

2.58
3.36
0.41
1.35
0.26
0.058
0.2
0.03
0.16
0.03
0.14
0.026
1.1
0.17
0.029

6.53
11.5
1.63
5.76
1.13
0.318
0.82
0.14
0.75
0.15
0.66
0.134
4.5
0.9
0.154

8.76
17
2.08
8.38
1.8
0.453
1.23
0.15
0.77
0.16
0.56
0.104
4
0.84
0.162

7.62
13.9
1.61
6.79
1.43
0.425
1.15
0.15
0.85
0.17
0.62
0.122
5.2
0.84
0.137

10.8
20.5
2.43
10.4
2.33
0.689
2.15
0.31
1.69
0.36
1.21
0.237
10.4
1.64
0.274

8.29
15.5
2.06
7.02
1.25
0.319
0.87
0.13
0.71
0.16
0.59
0.115
4
0.83
0.138

0.6
b.d.
b.d.
2.3
2.2
314
14
20
167
36
666
1,470
580
1,710
1,690
95,970
1,990
1,344
1,473
511
b.d.
0.3
b.d.
5.6
1.7
22
115
10
157
188
50
b.d.
b.d.
20
20
0.1
b.d.
b.d.
0.2
b.d.
230
1,550
1,450
1,010
2,870
2,010
18
19
7
32
1
3
0.8
b.d.
b.d.
b.d.
b.d.
b.d.
2.5
1.9
1.5
2
2.4
0.6
b.d.
0.2
b.d.
b.d.
0.1
b.d.
b.d.
3
4
b.d.
21
29
2.6
2
2.6
2.2
1.9
1
b.d.
b.d.
30
b.d.
40
60
23
b.d.
47
62
84
15
b.d.
2
1
2
b.d.
1
1
6.5
b.d.
b.d.
11.5
9.3
13
8
6
13
5
2
b.d.
b.d.
b.d.
b.d.
2
b.d.
669
564
310
592
60
83
0.2
0.14
0.14
0.12
0.14
0.06
1.61
1.3
1.08
1.38
0.72
0.31
0.72
0.33
0.75
4.03
0.61
0.82
0.51
0.45
0.79
0.68
0.77
0.35
132
73
42
148
21
32
3.3
1.6
20.3
0.8
1.7
6.1
430
260
360
460
80
50
95
68
59
70
87
18

AA I/BaEn
AA II
AA II
BOD3-113.7 BOD42-62.3 BOD3-125.4

0.6
8
287
370
0.1
25
30
b.d.
490
11
b.d.
2.2
0.1
3
2.1
b.d.
14
b.d.
0.8
8
b.d.
455
0.14
1.05
0.6
0.56
88
46
270
69

1
74
487
1,865
3.2
9
b.d.
0.3
410
10
0.9
2
b.d.
2
2.1
b.d.
354
2
2.1
11
5
641
0.15
1.24
2.7
0.57
94
0.5
120
65

b.d.
28
300
688
1.1
28
b.d.
b.d.
350
10
0.6
1.7
0.2
2
2
b.d.
14
b.d.
1.3
10
1
532
0.15
1.25
1.15
0.54
109
6.4
500
75

AA II
BOD3-46.9

AA II
BOD3-34.4

b.d.
1.9
56
141
396
1,390
1,458
1,736
0.2
0.7
12
28
b.d.
30
b.d.
0.2
710
1,460
48
58
b.d.
b.d.
2.8
3.3
b.d.
b.d.
4
9
3
2.9
b.d.
30
30
46
1
1
1.9
8.7
13
28
b.d.
4
931
1,717
0.19
0.21
1.78
2.41
2.52
4.41
0.63
1.25
174
259
7.9
2.2
1,070
290
98
99

1716

HIGH-SULFIDATION EPITHERMAL PYRITE-HOSTED

KING ETAu
AL.
ORE FORMATION, SANGIHE ISLAND, INDONESIA

1716
Table 2.

Porphyry
AA II
BOD3-27.3
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
Total
LOI

AA II
BOD3-79.5

AA II
BOD3-132.9

AA II
BOD3-41

AA II
BOD3-65.4

AA II/BaEn
BOD3-65.8

AA III
BOD1-115

AA III
BOD1-124.9

AA III
BOD3-122.6

(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)

7.08
1.029
24.05
19.86
0.005
0.03
0.12
1.22
3.49
0.43
98.86
41.55

65.52
0.485
6.24
14.38
0.006
b.d.
0.05
0.05
0.01
0.1
98.17
11.31

59.09
0.624
16.11
7.88
0.016
0.02
0.08
0.23
0.17
0.18
98.46
14.06

39.59
0.567
3.97
32.64
0.017
0.02
0.07
0.16
0.21
0.13
99.66
22.28

56.91
0.431
5.67
18.17
0.005
0.02
0.08
0.43
0.42
0.11
100
17.79

17.64
0.082
0.81
31.27
0.003
0.02
0.04
0.06
b.d.
b.d.
77.25
22.94

59.72
0.61
16.49
7.98
0.014
0.02
0.11
0.07
0.03
0.21
98.39
13.13

61.62
0.773
16.96
5.73
0.022
0.03
0.1
0.14
0.03
0.11
99.98
14.47

39.9
0.298
3.6
32.09
0.006
0.02
0.04
0.31
0.29
0.04
98.21
21.62

La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Y
Yb
Lu

(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)

16.8
31.1
3.44
13.5
2.4
0.496
1.53
0.19
0.95
0.2
0.71
0.14
5.3
1.06
0.183

8.97
15.8
2.12
7.48
1.34
0.368
0.88
0.12
0.65
0.13
0.6
0.123
4.2
0.9
0.15

11.4
22.1
2.59
11.2
2.45
0.854
1.96
0.24
1.23
0.26
0.99
0.184
6.9
1.35
0.218

10.4
19.4
2.68
9.94
2.19
0.68
1.77
0.22
1.14
0.22
0.83
0.144
6.6
1.02
0.164

8.48
15.4
2.08
7.45
1.4
0.415
1
0.15
0.77
0.18
0.74
0.151
5.1
1.07
0.174

6.84
5.76
0.53
1.48
0.35
0.18
0.76
0.05
0.17
0.03
0.13
0.022
1.7
0.16
0.028

12.1
24.7
2.84
12
2.44
0.616
1.59
0.2
1.04
0.23
0.78
0.142
6.2
1.17
0.23

9.83
17.9
2.1
8.17
1.56
0.784
1.19
0.2
1.25
0.28
0.99
0.18
7.1
1.42
0.28

3.87
5.81
0.71
2.53
0.53
0.181
0.49
0.06
0.28
0.06
0.24
0.044
1.8
0.31
0.055

Ag
As
Au
Ba
Bi
Co
Cr
Cs
Cu
Ga
Ge
Hf
In
Mo
Nb
Ni
Pb
Rb
Sb
Sc
Sn
Sr
Ta
Th
Tl
U
V
W
Zn
Zr

(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)

3.2
55
1,240
1,546
1.2
17
40
0.1
640
184
b.d.
4
0.2
12
4.2
20
149
2
8.8
35
5
2,840
0.3
3.8
3.81
5.45
410
5.3
310
141

b.d.
106
717
2,354
b.d.
53
30
b.d.
1,440
13
1.7
3.6
b.d.
18
2.4
20
b.d.
b.d.
34.4
10
3
682
0.21
1.66
0.93
1.91
69
2.1
40
109

b.d.
104
345
1,517
1.5
11
20
b.d.
180
18
0.7
2.1
b.d.
15
2.6
b.d.
17
b.d.
2.1
14
b.d.
1,060
0.2
1.85
1.53
1.45
157
0.8
120
95

1.6
442
1,310
2,519
0.7
25
30
b.d.
3,500
24
0.6
2.1
b.d.
11
2.2
30
11
1
35.6
10
6
655
0.17
1.52
0.49
0.84
91
3.4
70
55

2.8
311
1,080
4,145
0.3
26
30
b.d.
2,720
19
1.2
2.2
0.1
5
2.2
b.d.
181
1
24.6
9
4
571
0.16
1.33
4.59
0.51
59
12.9
300
73

3.7
2,500
1,280
106,900
0.3
54
30
b.d.
15,000
6
1.2
0.3
0.2
21
0.6
20
b.d.
1
120
2
6
1,109
0.04
0.32
0.07
0.25
17
1.6
190
9

b.d.
60
273
802
0.4
8
30
b.d.
70
13
3.7
2.4
b.d.
58
4.2
b.d.
74
b.d.
4.5
14
4
685
0.19
1.83
1.21
0.67
120
b.d.
360
89

1.1
125
130
1,609
1
10
20
0.3
90
19
2.1
2.8
b.d.
49
2.9
b.d.
120
b.d.
10.4
23
2
295
0.2
1.93
3.13
12.6
199
b.d.
960
101

4.5
242
1,760
13,280
0.6
111
30
0.3
2,470
8
0.6
1.1
0.1
38
1.5
50
28
2
27.7
5
3
411
0.1
0.52
0.4
0.4
36
2.5
b.d.
36

Note: The sample name indicates the drill hole number and the depth; samples are organized by lithology (porphyry or crystal tuff) and alteration-type
(IA = intermediate argillic, BaEn = barite-enargite veins, AA = advanced argillic; see text for description), identified based on petrographic observations,
bulk rock geochemistry and/or X-ray diffraction analyses

(Cont.)
Crystal Tuff
Least altered
IA I
PANTAI
BID70-61.7
58.37
0.546
15.2

63.89
0.627
11.62

IA I
BID39-41.2

65.1
0.706
12.71

IA II
IA II
IA II
IA II
IA II
IA II
BID43-39.5 BID26-102.5 BID15-84.2 BID18-144.5 BID18-183.2 BID23-68.6

29.58
1.423
26.73

66.18
0.587
12.6

60.58
0.68
14.96

58.02
0.771
16.24

56.54
0.796
17.84

56.83
0.852
18.21

IA II
BID26-58

56.02
0.667
15.5

47.52
0.902
19.49

5.59
0.132
2.86
7.02
2.79
1.1
0.2
99.55
5.74

9.89
0.005
0.04
0.06
0.04
0.26
0.15
98.27
11.69

8.13
0.005
0.03
0.07
0.04
0.02
0.16
98.77
11.81

18.12
0.004
0.06
0.11
0.07
0.05
0.43
98.61
22.04

5.45
0.017
0.99
0.33
0.04
3.55
0.16
99.88
9.97

6.7
0.023
1.04
0.38
0.03
3.79
0.17
99.07
10.72

7.15
0.018
0.96
0.14
0.07
4.29
0.15
99.25
11.44

6.92
0.015
1.86
0.45
0.06
2.12
0.23
98.31
11.47

6.79
0.027
0.84
0.8
0.06
2.41
0.2
99.5
12.49

6.86
0.019
1.15
0.57
0.06
4.17
0.14
100.5
15.38

6.34
0.025
0.68
0.62
0.09
6.09
0.23
98.29
16.31

12.5
24.6
3.13
12.8
2.96
1.03
2.89
0.48
2.87
0.6
1.81
0.283
6.6
1.97
0.331

7.53
14.6
1.52
6.08
1.05
0.352
0.73
0.12
0.81
0.21
0.75
0.136
6.1
1.09
0.205

9.05
18.6
2.13
8.82
1.88
0.595
1.36
0.17
0.86
0.19
0.71
0.135
5.5
1.1
0.209

10.5
16.1
1.35
3.57
0.39
0.2
0.32
0.05
0.32
0.09
0.37
0.079
2.4
0.75
0.173

6.12
11.7
1.46
6.05
1.98
0.581
2.46
0.46
2.94
0.61
1.79
0.277
17.7
1.92
0.322

6.04
13.5
1.69
7.94
2.51
0.84
3.12
0.57
3.59
0.73
2.19
0.344
21.7
2.4
0.411

8.04
18.3
2.52
11.1
2.98
0.858
3.11
0.55
3.39
0.69
2.04
0.324
19.2
2.39
0.435

10.3
21.5
2.83
12.2
3.37
0.947
3.49
0.58
3.58
0.77
2.38
0.37
21.6
2.62
0.445

10.5
21.7
2.93
12.4
3.36
1.09
3.58
0.63
3.9
0.81
2.36
0.379
22.2
2.67
0.466

11.9
23.3
3.04
12.6
2.91
0.891
2.97
0.52
3.28
0.68
2.04
0.319
19.2
2.25
0.374

12.7
25.6
3.33
14.1
3.51
1.1
3.74
0.65
4.01
0.82
2.42
0.382
22.4
2.64
0.452

b.d.
b.d.
b.d.
181
b.d.
14
20
1.5
30
14
1.5
2.3
b.d.
b.d.
2.7
b.d.
b.d.
21
b.d.
18
b.d.
367
0.17
1.83
0.1
0.77
171
2.4
130

IA I
BID24-101

60
89

0.6
10
57
664
0.4
8
b.d.
b.d.
200
8
1.4
2.1
b.d.
b.d.
2.7
b.d.
15
4
1.7
14
3
1,040
0.15
1.22
0.38
0.38
120
0.8
b.d.
72

b.d.
19
66
107
0.5
21
b.d.
b.d.
100
12
1.7
2.2
b.d.
10
2.4
b.d.
25
b.d.
b.d.
14
3
688
0.17
1.03
0.75
0.91
123
0.8
80
80

1.9
25
391
1,837
4.2
80
200
0.3
490
16
2
4.2
b.d.
19
4.9
30
55
3
4.1
18
11
3,854
0.3
1.73
0.39
0.59
222
2.4
b.d.

12.7
204
317
8,105
b.d.
16
20
1.1
160
14
0.8
1.9
b.d.
16
2.1
b.d.
1,080
79
12.7
21
2
184
0.13
1.29
4.04
5.01
178
3.6
3,450
67

6.5
43
27
2,045
b.d.
14
b.d.
2
40
14
0.6
2.2
b.d.
3
2.3
b.d.
44
82
9.7
26
b.d.
73
0.14
1.23
0.9
0.74
201
5.6
320
76

3.2
15
54
1,381
b.d.
14
b.d.
1.7
50
15
0.5
2.4
b.d.
b.d.
2.8
b.d.
54
93
1.8
29
b.d.
59
0.16
1.63
1.07
0.61
248
8.7
300
82

b.d.
9
21
130
b.d.
21
20
1.2
60
16
1.5
2.6
b.d.
3
2.7
b.d.
10
42
b.d.
25
b.d.
23
0.15
1.59
0.35
0.52
245
2
70
92

b.d.
10
13
139
b.d.
21
b.d.
1.3
80
17
1.7
2.4
b.d.
b.d.
3.1
b.d.
23
52
6.7
32
b.d.
47
0.16
5.43
0.28
1.84
285
1.3
320
85

b.d.
94
b.d.
749
b.d.
16
b.d.
3
60
15
0.7
2
b.d.
b.d.
2.3
b.d.
30
80
11.5
25
b.d.
54
0.12
1.31
3.85
0.6
221
b.d.
350
70

b.d.
118
b.d.
744
b.d.
18
b.d.
4.4
70
19
0.8
2.7
b.d.
b.d.
3.3
b.d.
b.d.
105
9.7
32
b.d.
61
0.18
1.85
2.83
0.65
283
b.d.
470
100

the compositions of the altered rocks to those of their leastaltered equivalents. This was done by making binary plots of
the data, and determining which element pairs were linearly
distributed, as such a distribution would correspond to a relatively constant mass ratio for the elements and could indicate
that they were immobile (e.g., MacLean and Kranidiotis,
1987; Warren et al., 2007; Agrawal et al., 2008). These plots
show that concentrations of pairs of the following elements,
Zr, Ti, Nb, Hf, and Ta, form linear arrays. However,
because Ti, Nb, and Ta are not incorporated into the same
minerals as Zr and Hf (Ti, Nb, and Ta occur in rutile and Zr
and Hf in zir- con), the linear variation of Zr with Ti was taken
as evidence of immobility (Fig. 9). Assuming that Zr and Ti
were immobile, the concentration of these elements in each
altered sample was normalized to their concentration in a
least altered sam- ple for each rock type using the method of
Grant (1986). To scale the changes for each element
proportionally so that the mass change for an unaltered rock
is zero, the concentration of each element was multiplied by
the ratio of the immobile element concentrations (Zr and Ti)
in the fresh rock to that in the altered rock. Values less than
unity indicate losses of ele- ments relative to their
concentrations in the unaltered rock, and values greater than
unity indicate gains (Fig. 10).
Three distinct patterns of relative gains and losses are
observed for advanced argillic alteration (the small size
of the data set precluded separate treatment of advanced
argillic I, II, and III alteration) and intermediate argillic I
(Bawone and Binebase) and II (Binebase) alteration (Fig.
10). As expected from the mineralogy, the advanced argillic
and intermediate argillic I samples were strongly depleted
in the major elements, Mn, Mg, Ca, and Na, moderately
depleted or unchanged in K, weakly depleted in Al and P,
and relatively undepleted in Si. Somewhat unexpectedly,
however, these samples appear to be enriched in Fe. As py II
1.6

BOD
BID
Least Altered

TiO2 (wt. %)

1.2

0.8

0.4

0
40

80

120

160

Zr (ppm)
Fig. 9. Plot showing the distribution of TiO2 and Zr in variably altered
rocks of the Bawone (BOD) and Binebase (BID) deposits. See the text for an
interpretation of the significance of these data. The Pearson correlation coefficient for both deposits (r) = 0.80.

commonly occurs in the form of blebs that filled pores created by advanced argillic and intermediate argillic I alteration (and thus postdated this alteration), we suspect that most
if not all of the apparent enrichment in Fe is an artifact due
to unavoidable inclusion of py II in the samples analyzed to
represent this alteration. The intermediate argillic alteration II samples were also depleted in Mn, Mg, Ca, P, and
particularly in Na, but appear to have conserved Al, Si, and
Fe. In contrast to advanced argillic and intermediate argillic
I alteration, these samples are strongly enriched in K. The
overall distribution of trace metals and semimetals (Au, Cu,
As, Ag, Cr, Co, Ni, Zn, Mo, Sn, Sb, Tl, W, and Pb)
indicates that they were added during all stages of alteration,
albeit in variable quantities (it should be noted that because
of the py II problem referred to above, the additions of Cu
and Au for advanced argillic and intermediate argillic I
alteration may be overestimated). However, whereas Rb and
Cs were depleted (or unchanged) and Sr added during
advanced argillic and intermediate argillic I alteration, the
opposite occurred dur- ing intermediate
argillic II
alteration, i.e., Sr was depleted and Rb and Cs enriched
(Fig. 10).
Both the advanced argillic and intermediate argillic I
altered rocks underwent substantial mass losses in all REEs,
with the degree of depletion increasing progressively with
atomic number from La to Dy and then decreasing progressively to Lu (Fig. 10). In contrast to advanced argillic and
intermediate argillic I alteration, the depletion of REEs during intermediate argillic II alteration was greatest for La and
decreased with atomic number to Gd with the exception of
Eu. We consider that the very small additions of the heavy
rare earth elements (HREEs: Tb, Dy, Ho, Er, Tm, Yb, Lu)
reflect uncertainties in the mass transfer calculations and that
these elements were immobile during alteration. The preferential leaching of the light rare earth elements (LREEs: La,
Ce, Pr, Nd) during intermediate argillic II alteration is consistent with results of experiments showing that the LREEs
are more mobile in chloride-bearing hydrothermal fluids than
the HREEs (Migdisov et al., 2009). The reason for the preferential depletion of Eu, Gd, Tb, Dy, and Ho during advanced
argillic and intermediate argillic I alteration is unclear. A
pos- sible explanation for this anomalous behavior is that
depletion of the LREEs was inhibited because of their
incorporation by sulfates and clay minerals (e.g., Miller et
al., 1982; Hopf,
1993; Fulignati et al., 1999; Karakaya, 2009), and that without this uptake they would have been more depleted, consistent with the experimental predictions (Migdisov et al.,
2009). The differential behavior of the REEs reported above
supports observations from active hydrothermal systems that
REE chemistry offers a useful tool for distinguishing alteration types (e.g., Michard, 1989; Fulignati et al., 1998, 1999;
Lottermoser, 1992; Lewis et al., 1997; Salan et al., 2011).
Ore mineral composition
The compositions of pyrite and enargite were analyzed
using a combination of electron microprobe (EMP) and laser
ablation-inductively coupled plasma-mass spectrometry (LAICP-MS). Quantitative electron microprobe analyses for Fe, S,
Cu, As, Sb, Co, Ni, Zn, Se, and Te were conducted on carboncoated samples at McGill University using a JEOL 8900
instru- ment equipped with five wavelength dispersive
spectrometers

Fe 2O3

K2 O

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

10
1

Ag Au

P2 O5

Na2 O

MgO

100

0.1
10

Fe 2O 3

1000
100

Sr

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Cs

0.1

Rb

MgO

CaO

MnO

0.01

1
Ag Au

Na2O

10
K 2O P 2O5

3
2

SiO2

10

0.1

0.1
10

K2 O

1000

10

1
0.1

Au Ag Cu As Sn

CaO

P2 O 5

100

1
Na2O

0.01

MgO

0.1

MnO

Fe 2O3

10
Al2O 3 SiO2

Intermediate Argillic II

1000

0.1

Al O

Intermediate Argillic I

0.01

CaO

MnO

0.1

SiO2

10
1

Al2O 3

Advanced Argillic

10

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

0.1

Fig. 10. Relative gains and losses of elements for advanced argillically altered rocks from Bawone (red), intermediate
argillically altered I porphyry and crystal tuffs from Bawone and Binebase (yellow) and intermediate argillically II altered
(purple) crystal tuffs from Binebase, calculated using the method of Grant (1986). A value of 1 indicates immobility, less
than
1 indicates a relative mass loss and greater than 1 indicates a relative mass gain.

(WDS). The operating conditions were an excitation potential

of 20 kV, a beam current of 50 nA and a spot-size of 2 m.
Analyses were standardized using pyrite (Fe, S), chalcopyrite
(Cu), AsNiCo (As, Ni, Co), CdTe (Cd, Te), sphalerite (Zn),
stibnite (Sb), and AgSe (Se) supplied by CANMET. In addition to quantitative spot analyses, the EMP was also used to
produce element maps for Cu, Fe, Se, and As. The operating
conditions were an excitation voltage of 20 kV, an operating
current of 90 nA, and a beam diameter of 2 m. The counting
time was 30 ms and the pixel size between 0.20 and 1.28 m.
The LA-ICP-MS analyses were conducted at the Geological Survey of Canada (pyrite) using a Photon Machines Nalyte
193 mm Excimer laser coupled to an Agilent Technologies
7700 Series ICP-MS, and at Universit de Chicoutimi (enargite) using an Excimer Resolution M-50 (Resonetics) Laser
coupled to an Agilent 7700x ICP-MS. The concentration of
Fe57, S34, Cu65, Au197, Se77, Te125, Ag107, As75, and Sb121 was
measured in both pyrite and enargite. Pyrite was also analyzed for Co59, Ni60, Pb208, Zn66, and Bi209. The ablation pits
ranged from 14 to 54 m in diameter, and the counting time
was 100 s (30 s of background, 70 s of ablation) for pyrite
and 90 s (30 s for background, 60 s of ablation) for enargite.

The concentrations of Fe and S determined by EMP analysis

were used as an internal standard for the LA-ICP-MS analyses of pyrite and enargite, respectively; GSE-IG, NIST 610
and Po689 were used as external standards for the analysis of
pyrite and GSE-1G, PS1 and JB5 for enargite.
Pyrite: The following trace elements were detected in pyrite
using the EMP: As, Co, Cu, Ni, Sb, Se, Te, and Zn (Table AI).
LA-ICP-MS analyses yielded results for these elements similar to those obtained with the EMP, and also detected Ag, Au,
Bi, and Pb (Table A2). Copper is the principal trace element
in both generations of pyrite followed by Co, As, and Pb in py
I or by Co, Pb, and As in py II. Significantly, both generations
of pyrite contain ppm levels of Au and Ag.
Pyrite I crystals are compositionally unzoned (Fig. 7B) and
have a wide inter- and intra-crystal range of Cu concentrations
(0.021.5 wt %); the median Cu concentration is 0.44 wt %
and the interquartile range (IQR) is 0.24 to 0.72 wt %. Cobalt
concentration is significantly lower, with a median of 62.5
ppm (IQR = 15.6206 ppm). The median As
concentration is
43.9 ppm (IQR = 15.683 ppm) and that of Pb is 59.6 ppm
(IQR = 9.579.7 ppm). As mentioned above, py I is auriferous and argentiferous. The median concentrations of Au and

Ag are 1.0 ppm (IQR = 0.61.5 ppm) and 9.1 ppm (IQR =
1.129.6 ppm), respectively. Somewhat surprisingly, the concentrations of Se and Te, elements that with As are commonly
elevated in auriferous pyrite (e.g., Fleet et al., 1993; Reich et
al., 2005), are relatively low with median values of 9.6 ppm
(IQR = 6.141.1 ppm) and 3.8 ppm (IQR = 2.210 ppm),
respectively (Table 3).
The concentrations of all trace elements detected in py I
are higher in py II. The median concentration of Cu in py II
is 1.1 wt % (IQR = 0.423.4 wt %) and the maximum concentration 6.0 wt % (EMP Analysis, Table A1). The median concentration of Co in py II is 148 ppm (IQR = 48.4533 ppm),
that of Pb is 69.9 ppm (IQR = 2.7557 ppm) and that of As
is
118 ppm (IQR = 16.1417 ppm). Unlike py I, the concentration of Te is relatively high, with a median value of 31.3 ppm
(IQR = 11143 ppm) and that of Se is significant, with a
median of 25.9 ppm (IQR = 12.8102 ppm). The maximum
Au concentration in py II is 13.6 ppm, and the median, 2.4
ppm (IQR = 0.93.2 ppm), and the Ag maximum
concentration is
1,273 ppm, and the median, 3.7 ppm (IQR = 1.419 ppm).
Although the concentrations of the trace elements, on average, are lower in py I than in py II, the interelement associations are similar. Binary plots (Fig. 11) and element maps
(Fig. 12) show that high Au concentrations in py I and II are
generally associated with elevated Cu, As, Ag, and Te, but
Au concentration may be high even if concentrations of
these elements are relatively low; this is especially true for
Ag and Te. Gold concentration
is almost entirely
independent of Se concentration and shows no correlation
with Co (or Ni, Sb, Zn, Pb, and Bi, which are not shown)
concentration. The inter-element correlations for Ag are
similar to those for gold, except that Ag and Te are negatively
correlated.
As mentioned above, py II is complexly compositionally
zoned and py I is unzoned. The backscatter electron images
indicate that this zonation reflects differences in concentrations of trace elements, mainly of Cu (Fig. 7A). Compositional

zoning was confirmed by quantitative spot analyses of py II,

which show that there are appreciable compositional variations within single crystals.
Copper concentrations show the largest variation between
growth zones, the distribution of which reveals a complex
history of growth, overgrowth, and resorption (Fig. 12). In
addition to this growth zoning, sector zoning is evident in the
distribution of Cu (i.e., within single growth zones there are
sharply defined sectors of higher and lower Cu concentration
corresponding to differences in the crystal faces presented).
The nature of the sector zoning varies considerably with the
crystal habit and is most easily observed in drusy crystals (Fig.
12).
Based on electron microprobe analyses, the Cu concentration of individual zones can range from as low as 0.12 to as
high as 6.0 wt %, and vary inversely with the concentration
of Fe. In some zones, high Cu concentration is matched by
an elevated concentration of As, but in others, the concentrations of the two elements do not correlate positively (Fig.
12D, F). In addition to As, the concentrations of Ni, Se, and
Te were measured across the transects. All three elements
show increases in concentration with elevated Cu concentration. Where the concentrations are consistently above the
detection limits, Ni, Se, and Te covary. In some pyrite
crystals, they covary with Cu, in others with As, and in some
crystals, with both.
Further insight into how trace elements in py II covary
is provided by LA-ICP-MS depth profiles through crystal
growth zones. Overall, the profiles show that zones enriched
in Cu are enriched in all trace elements, although the concentration of individual elements covaries with some, but not
all, of the elements analyzed. This is illustrated in Figure 13,
which shows the signal intensity (counts) for a suite of elements through three growth zones. From this figure, it is evident that the concentrations of Au, As, and Te covary (they all
decrease strongly in the central zone), that Cu, Co, Ni, Zn, Bi,

Table 3. Average Composition of Py I, Py II, and Enargite Based on LA-ICP-MS Analyses

Ag
(ppm)

As
(ppm)

Au
(ppm)

Bi
(ppm)

Co
(ppm)

Cu
(wt %)

Fe
(wt %)

Ni
(ppm)

Pb
(ppm)

S
(wt %)

Sb
(ppm)

Se
(ppm)

Py I

Mean
Median
Min
Max
1st quartile
3rd quartile

33.0
9.1
0.3
145.8
1.1
29.6

95.4
43.9
2.3
467.3
15.6
83.0

1.1
1.0
d.l.
2.5
0.6
1.5

10.1
3.9
0.1
47.9
1.0
13.3

117.1
62.5
0.1
404.3
15.6
206.1

0.4
0.3
d.l.
1.5
0.2
0.6

59.7
58.4
52.3
71.7
53.1
62.5

43.1
33.7
0.5
182.9
14.2
49.9

55.3
59.6
0.5
199.8
9.5
79.7

53.3
53.4
51.7
54.6
53.4
53.4

3.7
3.7
0.3
11.0
0.8
4.3

31.8
9.6
1.2
118.6
6.1
41.1

Py II

Mean
Median
Min
Max
1st quartile
3rd quartile

80.6
3.7
d.l.
1,273.2
1.4
19.0

329.7
117.6
0.8
1,636.6
16.1
417.2

3.0
2.4
d.l.
13.6
0.9
3.2

9.4
5.9
d.l.
43.2
3.0
13.9

3,015.6
148.0
d.l.
21,417.7
48.4
533.6

1.1
0.6
d.l.
4.4
0.3
1.6

48.6
49.0
30.9
76.1
40.7
54.5

138.3
40.3
0.1
800.2
11.8
124.2

511.8
69.9
0.1
7,205.3
2.7
557.2

52.3
52.6
48.3
55.2
52.1
53.6

10.7
3.7
0.1
169.6
2.2
8.7

121.0
25.9
0.7
640.1
12.8
102.1

Enargite Mean
Median
Min
Max
1st quartile
3rd quartile

101.6
108.5
31.1
214.5
52.7
114.9

13.5
13.4
11.8
15.5
12.5
14.2

0.5
0.6
0.1
0.8
0.4
0.7

33.8
33.2
24.9
45.8
28.8
37.2

0.0
0.0
0.0
0.1
0.0
0.1

32.7
32.7
32.7
32.7
32.7
32.7

6,410.8
5,527.7
4,273.7
9,543.1
4,876.6
8,167.5

3.1
3.2
1.8
5.5
2.6
3.4

Note: See digital Appendices 1 to 4 for raw data

Te
(ppm)
10.1
3.8
0.7
35.5
2.2
10.0

Zn
(ppm)
5.8
2.8
0.6
22.9
1.0
6.1

218.3
91.7
31.3
6.8
0.1
0.5
1,430.9 1,936.3
11.0
1.1
142.7
40.4
141.0
135.9
79.5
211.3
95.1
188.9

10-4

10-4

10-6

10-6

-1

10-1

10-3

10-3

10-5

Cu (afu)

10

Cu (afu)

10-2

As (afu)

Pyrite I
Pyrite II

10-2

10-5

10-3

10-7

10-7

10-5

10-3

Se (afu)

Te (afu)

10-5

10-5

10-5

Sb (afu)

Te (afu)

10-3

10-5
10-7

10-1

10-4

10-3

10-5

Co (afu)

Ag (afu)

10-7

10-5

-6

10

10-7

10-7
10-9

10-8

10-7

10-6

Au (afu)

10-8

10-7

10-6

10-5

10-4

Ag (afu)

Fig. 11. Binary plots of trace element concentration in pyrite analyzed by LA-ICP-MS and shown in atoms per formula
unit (afu).

and Se covary and do so independently of Au, As, and Te,

and that Ag and Pb covary independently of the other two
groups of elements. It should be noted, however, that these
group- ings are not observed in all crystals. For example, Te
behaves independently of Au and As in some crystals and
covaries with Se in others. Nonetheless, the Cu group of
Cu, Ni, and Co generally covaries independently of the Au
group of Au, As, and Te (Se). Silver concentration is
usually decoupled from those of both Au and Cu, and
commonly covaries with Pb, Bi and, rarely, Se concentration.
Enargite: On the basis of quantitative EMP analyses
(Table A3), enargite has close to an end member composition with a median As concentration of 18.5 wt % (IQR

= 18.118.8 wt %), a median S concentration of 32.8 wt %

(IQR = 32.733.0 wt %) and a median Cu concentration of
48.6 wt % (IQR = 48.148.8 wt %). The trace element concentrations were analyzed by a combination of EMP and LAICP-MS methods, and predictably, Sb was the trace element
with the highest concentration with a median of 5527 ppm
(IQR = 48768167 ppm; Tables 3, A4). This is well below its
concentration in stibioenargite (Springer, 1969; Maske and
Skinner, 1971; Posfai and Buseck, 1998). Iron is the next
most important trace element with a median concentration of
316 ppm (IQR = 117649 ppm), followed by Te and Se, with
median concentrations of 135 ppm (IQR = 95.1189 ppm)
and 3.2 ppm (IQR = 2.63.4 ppm), respectively (Table 3).
The

BSE Images

Cu map

Composite element maps

Ar
se
nic

Co
pp
er

Iro
n

F
Ar
se
nic

Co
pp
er

Iro
n

H
Se
le
ni
u
m
Co
pp
er

Iro
n

Au content is significantly lower than that of py I or py II, with

a median of 0.6 ppm (IQR = 0.40.7 ppm), but the median
silver content is significantly higher than that of either generation of Py (108 ppm, IQR = 52.7114.9 ppm). From BSE
images, the enargite appears to be unzoned (Fig. 8C), but LAsome
trace
elements
and
Cu small
(Fig. variations
13). Despite
the signals
presence
ICP-MS
depth
profiles
show
in the
of
of a number of trace elements in significant concentration in
the enargite, none of them display a systematic correlation
with another trace element.
Sulfur Isotopes
Isotopic compositions of pyrite and sulfate (alunite and barite) were measured to better understand the physiocochemical conditions of ore formation. In particular, they were used
to estimate temperature and assist in the interpretation of fO2
and pH conditions.
Method
Because it is impossible to physically separate the finegrained, intergrown pyrite and alunite, separation was
achieved chemically in two stages. In the first stage, finely
ground altered rock was reacted with a Cr-reducing solution to liberate H2S from the sulfides (Canfield et al., 1986).
This procedure stripped the sample of sulfide, allowing the
solid residue to be filtered and reacted with Thodes solution
(Thode et al., 1961) to convert the remaining sulfur (sulfate)
to H2S. In both cases, the resulting H2S was trapped using a
zinc-acetate solution and reacted with a solution of AgNO3
to produce solid Ag2S that was purified and reacted with SF6
(Thode and Rees, 1979) prior to introduction into a Thermo
Finnigan MAT 253 dual-inlet gas-source mass spectrometer
at McGill University for measurement of sulfur isotope ratios,
with IAEA-S-1 as an internal standard (Sharman, 2011). The
ratios are reported relative to V-CDT in notation.
Results
Two samples of argillically and advanced argillically altered
material and one sample of pyrite and barite from the late
barite-enargite veins were selected for sulfur isotope analysis
(Table 4). The sulfate concentration in the preliminary analysis was below the detection limit but consistent 34S values
were obtained for pyrite. The 33S, 34S, and 36S per mil values for pyrite average 2.65 ( 1s = 0.25), 5.17 ( 1s =
0.48), and 9.93 ( 1s = 0.77), respectively. The standard
deviations are small considering that the pyrite represents
different gen- erations of mineralization.

Table 4. Sulfur Isotope Compositions of Py I and Py II

from the Bawone and Binebase Deposits
Samples
BID16-66.3
BOD3-81.5
BOD1-99.4

PyI
PyII
PyI

33S

34S

36S

2.94
2.54
2.48

5.73
4.93
4.86

10.82
9.59
9.39

Note: The full analytical uncertainty (1s) for sulfur isotope analysis is
estimated to be 0.13 for 34S values, based on the long-term standard
deviation for repeat analyses of in-house standards

Discussion
Geologic setting
The Bawone and Binebase deposits occur at the southeastern end of a young volcanic island with an active volcano to
the northwest and a chain of extinct/dormant volcanic edifices
to the south. Both deposits are hosted by rocks of the Binebase Group, a thick andesitic sequence of alternating, interbedded porphyritic lava flows or epiclastic deposits and crystal
tuffs that were probably deposited in close proximity to a volcanic center. If, as seems likely, a volcano was located above
the Binebase and Bawone deposits (and was thus close to the
coast), its erosion would have been very rapid due to a combination of rising sea level (as indicated by the marine deposits
of the overlying Pinterang Formation), thermal subsidence as
the magmatic center moved northwest, and the hot, wet tropical climate. Consequently, all traces of the volcanic edifice
could have disappeared in tens of thousands of years.
Paleodepth and pressure
A very crude, approximate estimate of the depth and pressure of emplacement of the Bawone and Binebase deposits
can be made by comparing their current elevation to that of
the base of the crater of Awu volcano, the only active
volcano on Sangihe Island. This assumes that the volcano
overlying these deposits reached an elevation similar to that
of Awu vol- cano, and although this cannot be known, it is
suggested by the crater elevation of the somewhat larger
dormant/extinct Kaki- raeng volcano located immediately to
the west of the deposits. The elevation of the crater of this
volcano is 1,006 m (it has likely been reduced in height due
to erosion), whereas that of the crater of Awu volcano is
1,327 m (Fig. 1). By contrast, the Bawone and Binebase
deposits are exposed at elevations of 86 and 65 m,
respectively. Thus, if the crater of the volcano above the
deposits was at an elevation similar to those of Awu

Fig. 12. BSE images (A, C, E, G) and corresponding copper map (B) or composite Cu (green), Fe (blue) and As/Se (red)
maps (D, F, H) showing strong sector and growth zoning in py II. Brighter colors correspond to higher concentrations of the
given element. (A) BSE image of complex, m-scale, strongly growth zoned drusy pyrite overgrowing massive, porous pyrite,
also zoned. (B) Cu map of the same crystal, light blue-green represents higher Cu concentration; the darker the blue, the
lower is the Cu concentration. The growth zoning is perpendicular to the crystal growth direction and records the primary
growth history (50 m scale). (C, D) Drusy, py II with growth and sector zones and very high Cu concentrations (green)
and variably As-rich (red) bands transitioning outward into massive, porous py II with lower Cu concentration and isolated
zones of As enrichment (scale bar is 50 m). (E, F) Cross section is through a euhedral py II crystal displaying growth zoning
with alternating As (red) and Cu (green) enriched bands. Sector zoning most strongly evident as a Cu enrichment on three
equivalent faces about a three-fold axis (scale bar is 500 m). (G, H) Drusy py II crystals displaying complex growth zoning
in either Cu (green) or Se (red) bands. Sector zoning in Cu is also present in the form of a cross at the center of a cubic
pyrite grain, top-center (scale bar is 500 m).

Growth Zone 1

Growth Zone 2

Growth Zone 3

Co59

Signal Intensity (counts)

1 000 000

Fe57
Cu65
S34

100 000

Ni60

10 000

As75
Se77
1000

Te125
Bi209
Sb121

100

Au197

Zn66
Ag107

10

Pb208

50

100

150

200

250

Time (s)

Fig. 13. An example of a depth profile through three growth zones of a py II crystal produced by LA-ICP-MS, in counts
vs. time (depth) for major and trace elements. Arsenic, Te, and Au covary through the three growth zones and are
independent of Co, Cu, Ni, Zn, Se, and Bi, whereas Ag, Pb, and to some extent Sb covary independently of the other two
groups.

and Kakiraeng volcanoes, it follows that the deposits formed

at depths of approximately 900 to 1,300 m below the paleovent. These depths fall within the range of depths estimated
for other high-sulfidation epithermal deposits (Jannas et al.,
1990; Arribas, 1995; Cooke and Simmons, 2000). The depths
inferred for Bawone and Binebase (9001,300 m) correspond
to lithostatic pressures of 250 to 350 bars or hydrostatic pressures of 90 to 125 bars (assuming the water table was near the
paleosurface), respectively. As much of the mineralization is
disseminated and there is no evidence of large through-going
fractures that might have intersected the paleosurface, pressure was probably intermediate between the two extremes. In
the discussion that follows, we therefore assume that the pressure accompanying hydrothermal alteration and gold mineralization was ~200 bars.
Temperature and pH
Earlier, we showed that advanced argillic (AA) and
inter- mediate argillic (IA) alteration in the Bawone and
Binebase deposits are characterized by the following
mineral associa- tions: AA I (quartz + pyrite + pyrophyllite
natroalunite), AA II (quartz + pyrite natroalunite dickite
kaolinite), AA III (quartz + pyrite + kaolinite + alunite), IA I
(quartz + kaolinite
pyrite dickite), and IA II (quartz + illite pyrite). Here,
we use stability relationships among these minerals in the
system Al-Si-O-K-Na-Fe-H-S to make inferences about the
tempera- ture and pH of the fluids responsible for the
different types of

alteration (Figs. 14, 15). The total S concentration was

assumed to be 0.01 m, consistent with that inferred for other
high-sul- fidation epithermal systems (e.g., Muntean et al.,
1990). At a pH below 2, aluminum is mobile, an observation
confirmed by our mass balance calculations that provides
evidence for local Al mobility. For these conditions, Al activity
was assumed to be
0.1 (Knight, 1977; Fulignati et al., 1999). At higher pH, Al
was assumed to be immobile and its activity buffered by the
alumi- num silicate minerals (Stoffregen, 1987; Salvi et al.,
1998).The Na/K ratio was taken to be 10, assuming
equilibrium between natroalunite and alunite (natroalunite
and alunite commonly occur together but their textural
relationships could not be determined because of the very
fine-grained nature of the rock), and the conclusion that
alunite transformed to natroal- unite at a temperature of
~275C (see below). Oxygen fugac- ity was inferred from the
34S values for pyrite to be that of the hematite-magnetite
buffer (see below). The activities of Fe and Si were
assumed to have been buffered by pyrite and quartz,
respectively, which are ubiquitous in the deposits.
At the conditions for which Figures 14 and 15 were constructed, pyrite is stable above 250C (hematite is stable
below 250C), making this the lower temperature limit for all
alteration facies. Because kaolinite and quartz react to form
pyrophyllite at temperatures greater than 280C (Fig. 15), the
coexistence of quartz and kaolinite in AA II, AA III, and IA
I alteration zones constrains their temperatures to have been
less than 280C. Conversely, the presence of pyrophyllite in

400
And

350

Py
Na-Al

Pyr

300

T (C)

Mag

Albite

Musc

Microcline
Hem

Fe2+

250

Al

Range of alteration
conditions

Kao

200

AA I fields 1 & 2
AA II field 1
AA III fields 4 & 5

150

100

IA I field 5
IA II field 3

10

12

14

pH
Fig. 14. Stability relationships among minerals in the K-Na-Al-Si-O-H and Fe-S-O systems as a function of temperature
and pH. Also shown are the fields of stability of the five main alteration facies (shaded areas), advanced argillic I (AA I),
advanced argillic II (AA II), advanced argillic III (AA III), intermediate argillic I (IA I), and intermediate argillic II (IA II).
The diagram was calculated for 200 bar (SVP), log fO2 = 30, quartz saturation, Na+/K+ = 10, aS = 0.01 and aAl3+ = 0.1 (see
text for details). Silicate and sulfate species are shown by solid lines, Fe species by dashed lines and sulfur species by dotted
lines. The model was calculated using SULF34 (Zhang, 1993) and The Geochemists Workbench (GW; Bethke, 2005) with
thermodynamic data from Holland and Powell (1998), Stoffregen et al. (2000), Helgeson (1978), Robie and Hemingway
(1995), and Johnson et al. (1992).

the AA I alteration zone indicates that this alteration occurred

at a temperature above 275C (Holland, 1998). Natroalunite
is the stable form of the alunite group minerals in the AA I
alteration zone, and alunite is the stable form in the AA III
alteration zone. Unexpectedly, however, given the coexistence
of quartz and kaolinite (implying a temperature less than
280C), natroalunite is also the stable member of the alunite
family in the AA II alteration zone. We interpret this to indicate that AA II alteration occurred at ~280C, an interpretation that is supported by the presence of dickite in the AA II
alteration zone (kaolinite is widely inferred to convert to dickite above 150C: Hemley et al., 1969; Stoffregen and Alpers,
1987; Stoffregen and Cygan, 1990). In view of the
distribution of alunite group minerals among the AAI,
AAII, and AAIII zones, we conclude that alunite was
replaced by natroalunite at ~275C.
An upper temperature limit for AA I alteration is provided
by the absence of andalusite, which forms from the reaction
of pyrophyllite and quartz at ~340C (Figs. 14, 15). In
summary, we conclude that AA I alteration occurred at a
temperature between 275 and 340C, AA II alteration at
~275C, and AA III and IA I alteration at between about
250 and 275C. As

the IA II alteration association includes pyrite, this alteration

occurred at >250C and, although we cannot constrain the
upper temperature from its mineralogy, it is reasonable to
conclude that this limit was less than or similar to that for IA I
alteration, i.e., 275C.
On the basis of the stability relationships illustrated in Figure 14, specifically the presence of both natroalunite and
pyrophyllite in the AA I association, natroalunite and kaolinite/dickite in the AA II association, and alunite and kaolinite in
the AA III association, we interpret the pH of advanced argillic alteration to have been ~2.5. In principle, the pH could
have been significantly lower, if natroalunite and pyrophyllite
or alunite and kaolinite were not in equilibrium (Hemley and
Jones, 1964; Knight, 1977). If, however, the pH was below 2,
aluminum would have been highly mobile (Stoffregen, 1987),
which based on our analysis of mass changes (Fig. 10) was not
the case; aluminum experienced only minor depletion. This
supports a conclusion that the pH was at least 2 and more
likely 2.5. The presence of kaolinite in the IA I alteration
association constrains its pH to between 2.5 and 4, and the
presence of illite, but absence of K-feldspar and albite in the
IA II association, constrains its pH to between ~4 and 6.

HSO
4

2-

-20

250C 15

SO

Al

Kao

log fO2

-25

-30

Musc

10

Microcline

Hem

log fO2 (HM)

+
AlSO
4

Mag

-35

0
H2S

Py
Fe2+

Pr

-40
2

H
S-

-20

AlSO4+

300C

2SO
4

log fO2

-25

Na-Al

Pyr

Musc

SO2

10
5

Albite

Hem
Mag

-30

log fO2 (HM)

HSO- 4

pH

Py

-35
Fe+2

Pr

pH

H2S

-40
0

-5
H
S-

Fig. 15. Log fO2-pH diagrams showing stability relationships for minerals in the K-Na-Al-Si-O-H and Fe-S-O systems
(A) at 250C, and (B) at 300C. The diagrams were created assuming a pressure of 200 bar (SVP), quartz saturation, Na+/K+
= 10, aS = 0.01 and aAl3+ = 0.1 (see text for details). Silicates and sulfate species are shown by solid lines, Fe-species by
dashed lines and sulfur species by dotted lines. The red lines are 34SH2S contours at 1, 5 (the measured 34S value for
Sangihe pyrite) and 10, and constrain the range of log fO2 values for Au-Ag mineralization to approximately 32 (Fig 16A)
and 27 (Fig 16B) assuming a pH of 2.5 (see text for details). The term log fO2 (HM) refers to the number of log units of fO2
above or below that of the hematite-magnetite buffer (calculated using The Geochemists Workbench).

fO2
Ore-forming high-sulfidation epithermal systems are characteristically oxidizing, with oxygen fugacity straddling or just
below that of the hematite-magnetite buffer. For example,
val- ues for log fO2 (HM) reported for some other highsulfidation deposits have ranges of 4.24 to 1.32 (Thiersch et
al., 1997),
2.4 to 0.07 (Muntean et al., 1990) and <2.5 (Voudouris, 2011).
If the sulfur source were dominantly magmatic, which is considered to be the case for most high-sulfidation deposits (e.g.,
Muntean et al., 1990; Rye et al., 1992; Rye, 1993; Arribas,
1995;

Hedenquist et al., 1998b; Bethke et al., 2005; Deyell et al.,

2005a, b; Fifarek and Rye, 2005; Taylor, 2007), the 34S
value of the fluid would have been approximately zero. Using
this assumption, it is possible to calculate the 34S of the fluid
from the measured pyrite 34S values and, in turn, calculate
log fO2 for given pH values (Zhang, 1993). The negative 34S
values calculated for reduced sulfur (H2S) at Bawone and
Binebase, assuming a temperature between 250 and 340C,
are simi- lar to those of other high-sulfidation deposits
(Muntean et al., 1990; Hedenquist et al., 1994; Voudouris,
2010), and are consistent with sulfur isotope fractionation
between sulfides/

sulfosalts and sulfates in an oxidizing environment (Arribas,

1995; Cooke and Simmons, 2000). The log fO2 (HM) values
corresponding to the 34SH2S values for advanced and intermediate argillic alteration are between 4 and 1 (Fig. 15; Table 5;
Rye, 1993, 2005; Cooke and Simmons, 2000).
Metal transport
According to many researchers, there is a hyper-acidic
ground preparatory or pre-ore stage of hydrothermal alteration in high-sulfidation epithermal systems that precedes gold
mineralization and results in advanced argillic alteration (Stoffregen, 1987; Hedenquist et al., 1994, 1998, 2000; Arribas,
1995). There is also a consensus among these researchers that
the extreme acidity required to produce the advanced argillic
alteration that characterizes this ground preparation stage can
only be explained by interaction of the rocks with a
condensed acidic vapor (e.g., Hedenquist et al., 1994, 2000).
At Bawone and Binebase, the alteration does not reflect
interaction with fluids having the extreme acidity of some
high-sulfidation epithermal systems (residual vuggy silica is
not observed). Nonetheless, the very low pH of ~2.5
estimated for the fluid requires that it was a liquid condensed
from gas, as other fluids that might have been present in the
system, such as meteoric water/groundwater, seawater and
magmatic liquid would have had higher pH (Stoffregen and
Alpers, 1987; Meyer and Hem- ley, 1967; Hemley et al.,
1969; Stoffregen, 1987; White, 1957). Because advanced
argillic alteration involved crystallization of auriferous and
argentiferous pyrite (pyrite I) and this pyrite accounts for
between 30 and 50% of the hypogene Au (Ag-Cu)
mineralization in the Bawone and Binebase deposits, it therefore follows that much of the gold and the other metals were
introduced into the deposits by this condensed gas. Whether
or not pyrite II and enargite, which were introduced later, also
crystallized from this condensed gas is less clear but given the
similar trace element and isotopic compositions of pyrite I and
II, it is a strong possibility. There were also likely multiple
iter- ations of this process as porosity was created and
subsequently filled by alteration products (Berger and Henley,
2011).
Evidence that metals can be transported in high concentrations in magmatic vapors has been provided by analyses of
the compositions of vapor inclusions, which have yielded
poten- tially ore-forming concentrations of some metals,
including ppm levels of Au and Ag (Audtat et al., 1998,
2008; Ulrich et al., 1999; Williams-Jones and Heinrich, 2005;
Seo et al., 2009). In addition to the fluid inclusion data, there
is also a growing body of evidence from experiments that Au,
Ag and Cu can be transported in appreciable concentrations
in aqueous vapor (Migdisov et al., 1999; Archibald et al.,
2001, 2002; Migdisov and Williams-Jones, 2013; Hurtig and
Williams-Jones, 2014).
Table 5. Physicochemical Conditions for Each Alteration Facies Based
T
pH
log fO2 34
log fO2 (HM buffer)
on Stability Relationships Among Minerals and
S Values for
Py I and Py
II
IA I
260275
34
34 to 31
+1 to +3
IA II
>265
46
35 to 33
1 to +2
AA I
275330
0.54
28 to 27
+2 to +4
AA II
270275
0.54
28 to 27
+1 to +4
AA III
250270
0.54
33 to 32
+1 to +3

For example, Migdisov and Williams-Jones (2013) and Hurtig and Williams-Jones (2014) have shown that HCl-bearing
aqueous gases can dissolve ppm levels of Ag and Au, respectively, at temperatures as low as 400C. They have shown,
moreover, that the solubility of these metals increases exponentially with increasing f H2O. At the temperature and pressure predicted for the formation of the Bawone and Binbase
deposits, i.e., close to those of the H2O vapor-liquid boundary,
conditions would have been optimal for the transport of gold
and silver by magmatic vapor.
Direct evidence that condensed gases in environments
analogous to those of high-sulfidation epithermal deposits
can transport significant concentrations of metals is provided
by Kawah Ijen, an active volcano in eastern Java, Indonesia.
There, advanced argillic alteration (and residual silica alteration) is ongoing and accompanied by the crystallization of
pyrite enriched in Cu, Ag, and Au (Scher et al., 2013). The
fluid responsible for this alteration is a condensed magmatic
gas with a pH <1 containing ppm concentrations of Cu and
As (the concentrations of Au and Ag are below the level of
detection). Although the concentrations of Cu, Ag, and Au
in the Kawah Ijen pyrite are much lower than those in the
pyrite at Bawone and Binebase (because of the much lower
pressure and hence density of the gas), the metal ratios, e.g.,
Cu/Au and Ag/Au are very similar to those of the two Sangihe
Island deposits (Fig. 16). We can therefore conclude that the
two pyrite occurrences likely formed by the same process and
that the fluid which transported the ore metals in the Bawone
and Binebase deposits was therefore a magmatic gas. Several
other ore deposit studies have also documented gold mineralization associated with early advanced argillic alteration (e.g.,
Muntean et al., 1990; Voudouris, 2011).
Ore deposition
For the reasons presented above, we propose that the fluid
responsible for the formation of the Bawone and Binebase
deposits was a condensed magmatic gas. However, we consider it likely that this gas encountered a physicochemical
barrier, such as the water table or an impermeable cap rock.
This seems to have been the case for the deeper mineralization at Bawone (Figs. 3A, 6A), as the gas condensed to a lowpH liquid from which the ore mineral (pyrite) precipitated
or formed by replacement of primary iron-bearing minerals.
According to this interpretation, the ore metals were transported in the vapor as hydrated species, e.g., MeCl-H2O or
MeHS-H2O (Migdisov et al., 1999; Williams-Jones and Heinrich, 2005; Zezin et al., 2011b; Migdisov and Williams-Jones,
2013; Hurtig and Williams-Jones, 2014), whereas after condensation of the vapor to liquid, they would have been trans
ported as charged or neutral aqueous species like MeCl2 or
o
MeHS (Crerar and Barnes, 1976; Gammons and Barnes,
1989; Zotov et al., 1990; Gammons and Williams-Jones,
1997; Mountain and Seward, 2003; Stefnsson and Seward,
2004; Williams-Jones et al., 2009).
If saturation of the fluid with the metal had occurred, ore
deposition would have been controlled by reactions such as
the following:
Au(HS)o + H2O(l) = Au(s) + H2S + O2
AuCl2

+ H2O(l) = Au(s) +

2Cl

(1)
+

+ H + O2(g)

(2)

As (ppm)

Pyrite (Scher et al., 2013)

Pyrite I
Pyrite II

1000
100
10

Cu (ppm)

1000
100
10
1

Ag (ppm)

1000
100
10
1
0.1
0.01

0.0001

0.001

0.01

0.1

10

Au (ppm)
Fig. 16. Log-log plots comparing the trace element composition of py I
and py II with that of pyrite from an active high-sulfidation epithermal system
at Kawah Ijen volcano (Scher et al., 2013). From these plots, it is evident that
the ratios, Cu/Au and Ag/Au of py I and py II, and particularly the Ag/Au
ratio of py I, are broadly similar to those of Kawah Ijen pyrite.

However, as native gold does not occur in the deposits,

instead, the gold occurs with other metals as nanoparticles in
pyrite or within the structure of this mineral, it follows that
gold was undersaturated in the liquid.
Deposition of gold and other metals is interpreted to have
occurred as a result of their adsorption onto the faces of
pyrite during crystal growth. This deposition began at the
onset of advanced argillic alteration with the precipitation of
pyrite I and continued with the precipitation of pyrite II.
Adsorption of gold onto pyrite has been proposed previously
as a mecha- nism to explain the occurrence of invisible gold
in other epi- thermal deposits (e.g., Simon et al., 1999; Wilder
and Seward,
2002; Pals et al., 2003). It also has been investigated experimentally at ambient pressure and temperature for pH values
from 2 to 10. Results of these experiments for pyrite having
negatively charged crystal faces show that over 90% of the
gold in solution (undersaturated with respect to native gold)

is adsorbed at a pH <5 (Widler and Seward, 2002). Pyrite can

also have positively charged faces if arsenic bearing (Favorov
et al., 1974), but the effects of Cu on the surface properties of
pyrite are unknown.
Pyrite I is an integral part of advanced and intermediate
argillic alteration, and accounts for 30 to 50% of the gold in
the Bawone deposit and in the hypogene part of the Binebase deposit with an median concentration of 1.0 ppm Au;
the median concentrations of Ag and Cu are 9.1 ppm and
0.44 wt %, respectively. The texturally complex pyrite II contains median values of 2.4 ppm Au, 3.7 ppm Ag, and 1.1 wt %
Cu, and accounts for most of the remaining gold. Some gold
and even more silver are present in enargite (median values of
0.6 ppm Au and 108 ppm Ag).
Insights into the conditions favorable for the uptake of gold
by pyrite in the Bawone and Binebase deposits are afforded
by the presence of both growth and sector zoning in pyrite
II. The latter zoning reflects differences in the concentrations
of elements on two nonequivalent faces within single growth
zones, and enables partition coefficients to be calculated
for these faces, which record the relative changes in physicochemical conditions during crystal growth (van Hinsberg
and Schumacher, 2007). We have used analyses of sector and
growth zones in pyrite II to determine the conditions favorable for the incorporation of gold and other trace elements
into pyrite. The element concentrations in two adjacent
nonequivalent faces were measured for a series of growth
zones and the partition coefficients (Kd) were calculated. We
observed that the highest gold concentrations coincided with
periods of growth marked by relatively constant Kd, and lower
gold values coincided with sharp increases and decreases in
the Kd (Fig. 17). Thus, in contrast to mineralization produced
by saturation of an ore mineral, which is favored by rapid
changes in the physicochemical conditions due to processes
like mixing and boiling, concentration of gold in the Bawone
and Binebase deposits was favored when physicochemical
conditions were relatively stable.
Incorporation of trace elements in pyrite
Unlike many examples of deposits of invisible gold, the
pyrite in the Bawone and Binebase deposits contains only
trace quantities of As (Tables 3, A1, A2). Despite this low
concentration of As relative to that in auriferous pyrite from
other deposits (e.g., Reich et al., 2005), Au concentration correlates positively with the concentration of As (Figs. 11, 13,
16); the latter is a hundred times greater than the concentration of Au in py I and py II. This correlation suggests that
Au + As substituted for Fe, as has been proposed previously
for other deposits containing gold hosted in pyrite (Cook and
Chryssoulis, 1990; Fleet et al., 1993; Huston et al., 1995). It
is also possible, however, that some or all of the gold occurs
as nanoparticles within the pyrite. Although our data do not
allow us to determine whether the gold was incorporated into
the pyrite structure or is present as nanoparticles, Reich et al.
(2005) have observed that in pyrite with Au/As > 0.02, gold
occurs as microinclusions, whereas if the ratio is less than
this, it is substituted into the pyrite structure. The average
Au/As for pyrite in the Bawone and Binebase deposits is
0.019, sug- gesting that much of the gold may have been
incorporated in the structure of this mineral.

16.79

Kd
Cu light
Au (ppm)

11.46

12.22

Kd

Cu (wt %)

1
1
2.65

2.23

0
0

20

40

60

80

100

Distance
Fig. 17. A plot showing the variation in the partition coefficient (Kd; black line) and the concentration of Cu (red line)
as a function of the distance (in percent) from the core to the rim of a single pyrite crystal (BID34-84). In this plot, the Kd
corresponds to the ratio of the Cu concentration in one sector zone (the one with the higher overall Cu concentration, i.e.,
the light zone in BSE images, e.g., Fig. 13) to the Cu concentration in the adjacent sector zone (the dark zone), within
the same growth zone. The Kd is inferred to vary inversely with temperature following van Hinsberg and Schumacher (2007).
The yellow squares represent gold concentrations analyzed by LA-ICP-MS, with the width of the square corresponding to
the diameter of the pit in relation to the growth zones. The vertical scale on the right hand side of the diagram indicates the
Cu concentration. The highest gold concentrations correspond to regions where the Kd is stable, whereas lower gold concentrations correspond to intervals over which there is a rapid change in Kd values; Cu concentrations show the same behavior.

Incorporation of Au in the pyrite structure is also favored

by the presence of Te, which substitutes for the smaller S
ion, thereby expanding the lattice and providing space for the
large Au ion (Chouinard et al., 2005a; Bi et al., 2011). The
presence of appreciable Te (concentrations of Te are tens (py
I) to a hundred (py II) times greater than that of Au) and its
positive correlation with Au (Fig. 14) suggests that this substitution was also important in the uptake of Au.
Although the As concentration in pyrite II is low compared
to that of auriferous pyrite elsewhere, the Cu concentration is
anomalously high, up to 6 wt % Cu (Abraitis et al., 2004). Significantly, most of the other examples of auriferous pyrite
with high copper contents are also from high-sulfidation
epithermal deposits, e.g., Pascua Lama (up to 1.5 wt % Cu;
Chouinard et al., 2005a), Pueblo Viejo (up to 3.0 wt % Cu;
Deditius et al., 2011) and Chelopech (up to 4.5 wt % Cu;
Pacevski et al.,
2008). Moreover, the exceptions, such as pyrite from the Coka
Marin polymetallic deposit (up to 8 wt % Cu; Pacevski et al.,
2008) have many characteristics of high-sulfidation deposits.
It has been shown that copper can be incorporated in
the pyrite structure both as nanoparticles and by substitution for Fe, even within a single ore deposit such as Peublo

Viejo (Huston et al., 1995; Oberthr et al., 1997; Deditius et

al., 2011). However, there is no agreed upon mechanism to
explain the rare and anomalous Cu concentrations in pyrite.
Some studies have shown that Cu-rich pyrite is the result of
recrystallization of Cu-phases (Pacevski et al., 2008). This was
not the case at Bawone and Binebase because of the welldocumented zoning that records the growth history of the
crystals (Fig. 12). Other researchers have suggested oxidation
of aqueous Cu+ and direct substitution of Cu2+ for Fe2+ (e.g.,
Chouinard et al., 2005a; Pacevski et al., 2008) accompanied
by the incorporation of other trace elements that cause
distortion of the lattice (e.g., Radcliff and McSween, 1970).
Whatever the mechanism, it seems likely that the highly
oxidizing condi- tions that are characteristic of highsulfidation deposits play a role in the incorporation of Cu in
the pyrite structure.
Genetic model
We propose that the metals forming the Bawone and Binebase deposits originated from a relatively oxidized magma
that was emplaced at high crustal levels and exsolved a low
den- sity supercritical fluid (that subsequently evolved to
vapor) into which metals (including Au, Ag, and Cu)
partitioned

preferentially. The gold and other metals were transported

as hydrated species that ascended through the volcanic pile
via fractures and zones of enhanced permeability to depths
between 900 and 1,300 m, where the vapor condensed at temperatures between 250 and 340C to form an acidic liquid
with a pH of ~2.5; fO2 ranged up to four log units above the
hematite-magnetite buffer.
The acidic condensate altered the host andesite, replacing primary mafic minerals, such as hornblende, biotite, and
magnetite, with auriferous py I (sulfidation), and converting
feldspars to an advanced argillic alteration association that
includes kaolinite, pyrophyllite, alunite, natroalunite, and
dickite. If fluids had been previously neutralized by reactions
with rocks or fluid/rock ratios were lower, the alteration led
to an intermediate argillic I alteration association of kaolinite, quartz, and pyrite, and a distal intermediate argillic II
alteration association of illite, quartz, and pyrite. The alteration also created porosity through the dissolution of minerals.
During alteration, all major elements, except for Zr and Ti
were depleted proximal to the main alteration/mineralization

conduits (Al and particularly Si experienced only minor depletion; Fig. 10). Iron and many trace elements, except for the
REE, Rb and Cs, were enriched, in some cases by orders of
magnitude, relative to their original abundance.
Auriferous py II was deposited in veins and in open space
created by mineral dissolution. These same veins were fractured and the fractures filled by barite and enargite. Rare, late
auriferous (electrum) barite-base metal (sphalerite and chalcopyrite) veins formed at Binebase.
Py I, which is associated with advanced and intermediate
argillic alteration, and py II, precipitated under conditions
for which metals, including gold, were undersaturated in
the fluid. The metals, i.e., Au, Ag, and Cu, were adsorbed
onto the surfaces of the growing pyrite crystals and incorporated in the pyrite either as a solid solution or as nanoparticles. Some gold and silver were incorporated in enargite by
the same mechanisms (Fig. 18). The Bawone and Binbase
deposits were subsequently exhumed and partially oxidized,
creating an upper zone of supergene-enriched oxide ore and
deeper lower-grade hypogene ores.

Impermeable

AuHS . nH2O

H2 SO42AuCl

AuHSo

H O
2

Impermeable
Advanced Argillic

AuHS . nH 2O

H SO
2

24

AuCl2 Cu

Cu

CuHS . nH 2O
AuCl2 . nH 2O

Cu

Py II Ba-En veins

Pyrite
Au

AgCl . nH 2O
H2S

CO2

SO2
H2O

Argillic

CuHS. nH2O

AuHSo

Fig. 18. A cartoon cross section through the stratovolcano that may have hosted the Bawone and Binebase gold deposits.
Moderately dipping flows and volcaniclastic units with variable porosity and permeability are crosscut by structures that
permitted transfer of heat and fluids (red) upward. The latter caused hydrothermal alteration of the adjacent rocks (pink).
Some of the conduits vented at the surface, producing solfataras, whereas others terminated at impermeable barriers, such as
the welded andesite tuff in the Bawone deposit, or at perched water tables corresponding to permeable and less permeable/
impermeable layers. The small circle in the cross section indicates the location of the large circles, labeled A to C. Circle A
illustrates the transport of the metals as hydrated species in magmatic vapor rising through the volcanic pile and condensing at
an impermeable boundary. Circle B shows the distribution of rocks altered by highly acidic condensed vapor, and the
accom- panying pyrite-hosted gold (copper, silver) mineralization. Finally, Circle C depicts a pyrite crystal with two types
of faces onto which copper and gold adsorbed preferentially from a gold-undersaturated condensed vapor to produce gold
(copper, silver)-rich sector- and growth-zoned pyrite II. Multiple iterations of this process are likely required to produce an
economic high-sulfidation deposit of this style.

Conclusions
Textural and geochemical observations provide compelling evidence that the Bawone and Binebase gold deposits
were the products of a condensed acidic magmatic vapor.
This fluid produced the advanced argillic and intermediate
argillic alteration that is characteristic of high-sulfidation epithermal systems and deposited gold, as well as copper and
silver, either within the structure of pyrite or as nanoparticles
within this mineral. The fluid did not deposit native gold or
electrum (except in very late veins at Binebase) and so we
conclude that it was undersaturated in respect to these metals. Instead of precipitating directly from the fluid, gold and
silver were concentrated by adsorption onto the surfaces of
growing pyrite (and to a much lesser extent enargite) crystals,
where they either formed nanoparticles or substituted for iron
in the structure of the mineral. Much of the auriferous pyrite
formed during advanced and intermediate argillic alteration
as a result of the sulfidation of primary mafic minerals. Auriferous pyrite (py II) crystallized later, filling fractures in the
earlier formed pyrite, and was joined even later by Au-Ag
bearing enargite that precipitated in reopened pyrite II veins.
Although the later pyrite II is richer in Au than pyrite I, and
enargite is richer in Ag than both pyrite generations, the precious metals in both minerals are interpreted to have concentrated from a condensed magmatic vapor by adsorption
during crystal growth. The Bawone and Binebase deposits are
part of the continuum of high-sulfidation deposits, formed
from a condensed magmatic vapor, and record a mineralizing
process that likely has contributed to the formation of many
other high-sulfidation deposits.
Acknowledgments
The authors thank East Asia Minerals for their financial and
logistical support, in particular Tom Mulja for suggesting the
project and for his assistance and comments. The field component of the research would not have been possible without
the help of Arodji Wisanggono, Johnnedy Situmorang, Mardy
Posumah, Grace Kapal, and the staff on Sangihe Island and
in Jakarta. Simon Jackson and Jeanne Percival at the GSC,
Boswell Wing and Libby Sharman of the Sulfur Isotope laboratory at McGill University, Lang Shi and Jeanne Paquette
provided invaluable assistance with the analytical aspects of
the research. The project was funded by East Asia Minerals
and an NSERC-CRD grant to A.E. Williams-Jones and G.
Williams-Jones with additional support by DIVEX. Constructive reviews by R. Fifarek, R.W. Henley, and associate editor
D. John improved the paper considerably.
REFERENCES
Abraitis, P.K., Pattrick, R.A.D., and Vaughan, D.J., 2004, Variations in the
compositional, textural and electrical properties of natural pyrite: A review:
International Journal of Mineral Processing, v. 74, p. 4159.
Agrawal, S., Guevara, M., and Verma, S., 2008, Tectonic discrimination of
basic and ultrabasic volcanic rocks through log-transformed ratios of immobile trace elements: International Geology Review, v. 50, p. 10571079.
Archibald, S., Migdisov, A.A., and Williams-Jones, A.E., 2001, The stability
of Au-chloride complexes in water vapor at elevated temperatures and
pres- sures: Geochimica et Cosmochimica Acta, v. 65, p. 44134423.
Archibald, S.M., Migdisov, A.A., and Williams-Jones, A.E., 2002, An experimental study of the stability of copper chloride complexes in water vapor at
elevated temperatures and pressures: Geochimica et Cosmochimica Acta,
v. 66, p. 16111619.

Arribas, A.R., 1995, Characteristics of high-sulphidation epithermal deposits,

and their relation to magmatic fluid, in Thompson, J.F.H. ed., Magmas,
fluids, and ore deposits, Mineralogical Association of Canada, Short Course,
v. 23, p. 419454.
Audtat, A., Gnther, D., and Heinrich, C.A., 1998, Formation of a magmatic-hydrothermal ore deposit: Insights with LA-ICP-MS analysis of fluid
inclusions: Science, v. 279, p. 20912094.
Audtat, A., Pettke, T., Heinrich, C.A., and Bodnar, R.J., 2008, Special
Paper: The composition of magmatic-hydrothermal fluids in barren and
mineral- ized intrusions: Economic Geology, v. 103, p. 877908.
Beaulieu, S., 2010, InterRidge global database of active submarine hydrothermal vent fields: prepared for InterRidge, Version 2.0: World Wide
Web electronic publication, http://www.interridge.org.IRvents.
Berger, B.R., and Henley, R.W., 2011, Magmatic-vapor expansion and the
for- mation of high-sulfidation gold deposits: Structural controls on
hydrother- mal alteration and ore mineralization: Ore Geology Reviews, v. 39,
p. 7590. Bethke, C.M., 2005, The Geochemists Workbench Release 6.0:
GWB Essentials Guide: University of Illinois: Urbana, Illinois.
Bethke, P.M., Rye, R.O., Stoffregen, R.E., and Vikre, P.G., 2005, Evolution
of the magmatic-hydrothermal acid-sulfate system at Summitville, Colorado: Integration of geological, stable-isotope, and fluid-inclusion evidence:
Chemical Geology, v. 215, p. 281315.
Bi, S.-J., Li, J.-W., Zhou, M.-F., and Li, Z.-K., 2011, Gold distribution in
As- deficient pyrite and telluride mineralogy of the Yangzhaiyu gold
deposit, Xiaoqinling district, southern North China craton: Mineralium
Deposita, v. 46, p. 925941.
Canfield, D.E., Raiswell, R., Westrich, J.T., Reaves, C.M., and Berner, R.A.,
1986, The use of chromium reduction in the analysis of reduced inorganic
sulfur in sediments and shales: Chemical Geology, v. 54, p. 149155.
Chouinard, A., Paquette, J., and Williams-Jones, A.E., 2005a, Crystallographic controls on trace-element incorporation in auriferous pyrite from
the Pascua epithermal high-sulphidation deposit, Chile-Argentina: The
Canadian Mineralogist, v. 43, p. 951963.
Chouinard, A., Williams-Jones, A.E., Leonardson, R.W., Hodgson, C.J.,
Silva, P., Tellez, C., Vega, J., and Rojas, F., 2005b, Geology and genesis
of the multistage high-sulfidation epithermal Pascua Au-Ag-Cu deposit,
Chile and Argentina: Economic Geology, v. 100, p. 463490.
Cook, N.J., and Chryssoulis, S.L., 1990, Concentrations of invisible gold in
the common sulfides: The Canadian Mineralogist, v. 28, p. 116.
Cooke, D.R., and Simmons, S.F., 2000, Characteristics and genesis of epithermal gold deposits: Reviews in Economic Geology, v. 13, p. 221244.
Crerar, D.A., and Barnes, H.L., 1976, Ore solution chemistry; V, Solubilities
of chalcopyrite and chalcocite assemblages in hydrothermal solution at 200
to 350C: Economic Geology, v. 71, p. 772794.
Deditius, A.P., Utsunomiya, S., Renock, D., Ewing, R., Ramana, C., Becker,
U., and Kesler, S.E., 2008, A proposed new type of arsenian pyrite: Composition, nanostructure and geological significance: Geochimica et Cosmochimica Acta, v. 72, p. 29192933.
Deditius, A.P., Utsunomiya, S., Ewing, R.C., Chryssoulis, S.L., Venter, D.,
and Kesler, S.E., 2009, Decoupled geochemical behavior of As and Cu in
hydrothermal systems: Geology, v. 37, p. 707710.
Deditius, A.P., Utsunomiya, S., Reich, M., Kesler, S.E., Ewing, R.C., Hough,
R., and Walshe, J., 2011, Trace metal nanoparticles in pyrite: Ore Geology
Reviews, v. 42, p. 3246.
de Vos, J., van den Hoek Ostende, L.W., and van den Bergh, G.D., 2007,
Pattern in insular evolution of mammals: A key to island palaeogeography,
in Renema, W. ed., Biogeography, Time, and Place: Distributions, barriers,
and islands: Dordrecht, The Netherlands, Springer, p. 315345.
Deyell, C.L., 2005a, Alunite in the Pascua-Lama high-sulfidation deposit:
Constraints on alteration and ore deposition using stable isotope geochemistry: Economic Geology, v. 100, p. 131148.
Deyell, C.L., Rye, R.O., Landis, G.P., and Bissig, T., 2005b, Alunite and the
role of magmatic fluids in the Tambo high-sulfidation deposit, El Indio
Pascua belt, Chile: Chemical Geology, v. 215, p. 185218.
Favorov, V.A., Krasnikov, V.I., and Sychugov, V.S., 1974, Variations in
semi- conductor properties of pyrite and arsenopyrite and their
determinants: International Geology Review, v. 16, p. 385394.
Fifarek, R.H., and Rye, R.O., 2005, Stable-isotope geochemistry of the Pierina high-sulfidation AuAg deposit, Peru: Influence of hydrodynamics on
SO42H2S sulfur isotopic exchange in magmatic-steam and steam-heated
environments: Chemical Geology, v. 215, p. 253279.
Fleet, M.E., Chryssoulis, S.L., MacLean, P.J., Davidson, R., and Weisener,
C.G., 1993, Arsenian pyrite from gold deposits: Au and As distribution

investigated by SIMS and EMP, and color staining and surface oxidation
by
XPS and LIMS: The Canadian Mineralogist, v. 31, p. 1
17.
Fulignati, P., Gioncada, A., and Sbrana, A., 1998, Geologic model of the magmatic-hydrothermal system of Vulcano (Aeolian Islands, Italy): Mineralogy
and Petrology, v. 62, p. 195222.
Fulignati, P., Gioncada, A., and Sbrana, A., 1999, Rare-earth element
(REE) behaviour in the alteration facies of the active magmatichydrothermal sys- tem of Vulcano (Aeolian Islands Italy): Journal of
Volcanology and Geother- mal Research, v. 88, p. 325342.
Gammons, C.H., and Barnes, H.L., 1989, The solubility of Ag2S in near-neutral aqueous sulfide solutions at 25 to 300C: Geochimica et Cosmochimica
Acta, v. 53, p. 279
290.
Gammons, C.H., and Williams-Jones, A.E., 1997, Chemical mobility of gold
in the porphyry-epithermal environment: Economic Geology, v. 92, p. 45
59. Garwin, S.L., 1990, South Sangihe Regional Reconnaissance
Program:
Jakarta, Indonesia, Report for P.T. Meares Soputan Mining, 84 p.
Grant, A., 1986, The isocon diagram: A simple solution to Gresens equation
for metasomatic alteration: Economic Geology, v. 81, p. 19761982.
Hall, R., 1996, Reconstructing Cenozoic Southeast Asia, in Hall, R., and
Blundell, D. eds., Tectonic evolution of Southeast Asia: Geological Society,
London, Special Publication 106, p. 153184.
2000, Neogene history of collision in the Halmahera region, Indonesia,
in Proceedings of the Indonesian Petroleum Association 27th Annual Convention, Jakarta, Indonesia, p. 487493.
Hedenquist, J.W., Matsuhisa, Y., Izawa, E., White, N.C., Giggenbach, W.F.,
and Aoki, M., 1994, Geology, geochemistry, and origin of high sulfidation
Cu-Au mineralization in the Nansatsu district, Japan: Economic Geology, v. 89, p. l30.
Hedenquist, J.W., Arribas, A.R., and Reynolds, J.T., 1998, Evolution of an
intrusion-centered hydrothermal system: Far Southeast-Lepanto porphyry
and epithermal Cu-Au deposits, Philippines: Economic Geology, v. 93,
p. 373404.
Hedenquist, J.W., Arribas, A.R., and Gonzalez-Urien, E., 2000, Exploration for epithermal ore deposits: Reviews in Economic Geology, v. 13, p.
245277.
Heinrich, C.A., Gnther, D., Audtat, A., Ulrich, T., and Frischknecht, R.,
1999, Metal fractionation between magmatic brine and vapor, determined
by microanalysis of fluid inclusions: Geology, v. 27, p. 755758.
Helgeson, H.C., 1978, Summary and critique of the thermodynamic properties of rock-forming minerals: American Journal of Science, v. 278, p. 1229.
Hemley, J.J., Hostetler, P.B., Gude, A.J., and Mountjoy, W.T., 1969,
Some
stability relations of alunite: Economic Geology, v. 64, p. 599612.
Hemley, J.J., and Jones, W.R., 1964, Chemical aspects of hydrothermal
alteration with emphasis on hydrogen metasomatism: Economic Geology, v.
59, p. 538569.
Henley, R.W., and Berger, B.R., 2011, Magmatic-vapor expansion and the
formation of high-sulfidation gold deposits: Chemical controls on alteration
and mineralization: Ore Geology Reviews, v. 39, p. 6374.
Holland, T.J.B., and Powell, R., 1998, An internally consistent thermodynamic data set for phases of petrological interest: Journal of Metamorphic
Geology, v. 16, p. 309343.
Hopf, S., 1993, Behaviour of rare earth elements in geothermal systems of
New Zealand: Journal of Geochemical Exploration, v. 47, p. 333357.
Hurtig, N., and Williams-Jones, A.E., 2014, An experimental study of the
transport of gold through hydration of AuCl in aqueous vapour and vapourlike fluids: Geochimica et Cosmochimica Acta, v. 127, p. 305325.
Huston, D.L., Sie, S.H., Suter, G.F., Cooke, D.R., and Both, R.A., 1995,
Sulfide deposits: Part I. Proton microprobe analyses of pyrite, and part II.
Selenium levels in pyrite: Comparison with 34S values and implications
for the source of sulfur in volcanogenic hydrothermal systems: Economic
Geology, v. 90, p. 11671196.
Jannas, R.R., Beane, R.E., and Ahler, B.A., 1990, Gold and copper mineralization at the El Indio deposit, Chile: Journal of Geochemical Exploration,
v. 36, p. 233266.
Johnson, J.W., Oelkers, E.H., and Helgeson, H.C., 1992, SUPCRT92: A software package for calculating the standard molal thermodynamic properties
of minerals, gases, aqueous species, and reactions from 1 to 5000 bar and 0
to 1000C: Computers & Geosciences, v. 18, p. 899947.
Karakaya, N., 2009, REE and HFS element behaviour in the alteration facies
of the Erenler
Dag Volcanics (Konya, Turkey) and kaolinite
occurrence: Journal of Geochemical Exploration, v. 101, p. 185208.
Kesler, S.E., Russell, N., Seaward, M., Rivera, J., McCurdy, K., Cumming,

G.L., and Sutter, J.F., 1981, Geology and geochemistry of sulfide mineralization underlying the Pueblo Viejo gold-silver oxide deposit, Dominican
Republic: Economic Geology, v. 76, p. 10961117.
Knight, J.E., 1977, A thermochemical study of alunite, enargite, luzonite, and
tennantite deposits: Economic Geology, v. 72, p. 13211336.
Landtwing, M.R., Furrer, C.F., Redmond, P.B., Pettke, T., Guillong, M.,
and Heinrich, C.A., 2010, The Bingham Canyon porphyry Cu-Mo-Au
deposit: III. Zoned copper-gold ore deposition by magmatic vapor
expansion: Eco- nomic Geology, v. 105, p. 91118.
Lewis, A.J., Palmer, M.R., Sturchio, N.C., and Kemp, A.J., 1997, The rare
earth element geochemistry of acid-sulphate and acid-sulphate-chloride
geothermal systems from Yellowstone National Park, Wyoming, USA: Geochimica et Cosmochimica Acta, v. 61, p. 695706.
Lottermoser, B.G., 1992, Rare earth elements and hydrothermal ore formation processes: Ore Geology Reviews, v. 7, p. 2541.
MacLean, W.H., and Kranidiotis, P., 1987, Immobile elements as monitors
of mass transfer in hydrothermal alteration: Phelps Dodge massive sulfide
deposit, Matagami, Quebec: Economic Geology, v. 82, p. 951962.
Maske, S., and Skinner, B.J., 1971, Studies of the sulfosalts of copper: I.
Phases and phase relations in the system Cu-As-S: Economic Geology,
v. 66, p. 901918.
Mavrogenes, J., Henley, R.W., Reyes, A.G., and Berger, B., 2010, Sulfosalt
melts: Evidence of high-temperature vapor transport of metals in the formation of high-sulfidation lode gold deposits: Economic Geology, v.
105, p. 257262.
Meyer, C., and Hemley, J., 1967, Wall rock alteration, in Barnes, H.L., ed.,
Geochemistry of hydrothermal ore deposits: New York, Holt, Rinehart, and
Winston, p. 166234.
Michard, A., 1989, Rare earth element systematics in hydrothermal fluids:
Geochimica et Cosmochimica Acta, v. 53, p. 745750.
Migdisov, A.A., and Williams-Jones, A.E., 2013, A predictive model for transport of silver chloride by aqueous vapor in ore-forming magmatic-hydrothermal systems: Geochimica et Cosmochimica Actamica, v. 104, p. 123135.
Migdisov, A.A., Williams-Jones, A.E., and Suleimenov, O.M., 1999,
Solubility of chlorargyrite (AgCl) in water vapor at elevated temperatures
and pres- sures: Geochimica et Cosmochimica Acta, v. 63, p. 38173827.
Migdisov, A.A., Williams-Jones, A.E., and Wagner, T., 2009, An
experimental study of the solubility and speciation of the rare earth
elements (III) in fluo- ride- and chloride-bearing aqueous solutions at
temperatures up to 300C: Geochimica et Cosmochimica Acta, v. 73, p.
70877109.
Miller, S.E., Heath, G.R., and Gonzalez, R.D., 1982, Effects of temperature
on the sorption of lanthanides by montmorillonite: Clays and Clay Minerals,
v. 30, p. 111122.
Moritz, R., Kouzmanov, K., and Petrunov, R., 2004, Late Cretaceous Cu-Au
epithermal deposits of the Panagyurishte district, Srednogorie zone, Bulgaria: Swiss Bulletin of Mineralogy and Petrology, v. 84, p. 7999.
Morrice, M.G., and Gill, J.B., 1986, Spatial patterns in the mineraloogy of
island arc magma series: Sangihe Arc, Indonesia: Journal of Volcanology
and Geothermal Research, v. 29, p. 311353.
Morrice, M.G., Jezek, P.A., Gill, J.B., Whitford, D.J., and Monoarfa, M.,
1983, An introduction to the Sangihe Arc: Volcanism accompanying arc-arc
collision in the Molucca Sea, Indonesia: Journal of Volcanology and Geothermal Research, v. 19, p. 135165.
Mountain, B.W., and Seward, T.M., 2003, Hydrosulfide/sulfide complexes of
copper (I): Experimental confirmation of the stoichiometry and stability of
Cu (HS)2 to elevated temperatures: Geochimica et Cosmochimica Acta, v.
67, p. 30053014.
Muntean, J.L., Kesler, S.E., and Russell, N., 1990, Evolution of the Monte
Negro acid sulfate Au-Ag deposit, Pueblo Viejo, Dominican Republic:
Important factors in grade development: Economic Geology, v. 85, p.
17381758.
Oberthr,
T., Weiser, T., Amanor, J., and Chryssoulis, S., 1997,
Mineralogi- cal setting and distribution of gold in quartz veins and sulfide
ores of the Ashanti mine and other deposits in the Ashanti belt of
Ghana: Genetic implications: Mineralium Deposita, v. 32, p. 215.
Pacevski, A., Libowitzky, E., Zivkovic, P., Dimitrijevic, R., and Cvetkovic, L.,
2008, Copper-bearing pyrite from the Coka Marin polymetallic deposit,
Serbia: Mineral inclusions or true solid-solution?: The Canadian Mineralogist, v. 46, p. 249261.
Pals, D.W., Spry, P.G., and Chryssoulis, S.L., 2003, Invisible gold and tellurium in arsenic-rich pyrite from the Emperor gold deposit, Fiji: Implications for gold distribution and deposition: Economic Geology, v. 98, p.
479493.

Posfai, M., and Buseck, P.R., 1998, Relationships between microstructure

and composition in enargite and luzonite: The American Mineralogist, v.
83, p. 373382.
Radcliff, D., and McSween, H.T., 1970, Copper zoning in pyrite from Cerro
de Pasco, Peru: Reply: The American Mineralogist, v. 55, p. 527528.
Reich, M.R., Kesler, S.E., Utsunomiya, S., Palenik, C.S., Chryssoulis, S.L.,
and Ewing, R., 2005, Solubility of gold in arsenian pyrite: Geochimica et
Cosmochimica Acta, v. 69, p. 27812796.
Robie, R.A., and Hemingway, B.S., 1995, Thermodynamic properties of minerals and related substances at 298.15 K and 1 Bar (105 Pascals) pressure
and at higher temperatures: U.S. Geological Survey Bulletin 2131, p. 461.
Rye, R.O., 1993, The evolution of magmatic fluids in the epithermal environment: The stable isotope perspective: Economic Geology, v. 88, p.
733752.
2005, A review of the stable-isotope geochemistry of sulfate minerals in
selected igneous environments and related hydrothermal systems: Chemical Geology, v. 215, p. 536.
Rye, R.O., Bethke, P.M., and Wasserman, M.D., 1992, The stable isotope
geochemistry of acid sulfate alteration: Economic Geology, v. 87, p.
225262.
Salan, A., Villemant, B., Grard, M., Komorowski, J.-C., and Michel, A.,
2011, Hydrothermal alteration in andesitic volcanoes: Trace element
redistribution in active and ancient hydrothermal systems of Guadeloupe
(Lesser Antilles): Journal of Geochemical Exploration, v. 111, p. 5983.
Salvi, S., Pokrovski, G.S., and Schott, J., 1998, Experimental investigation of
aluminum-silica aqueous complexing at 300C: Chemical Geology, v. 151,
p. 5167.
Scher, S., Williams-Jones, A.E., and Williams-Jones, G., 2013, Fumarolic
activity, acid-sulfate alteration, and high sulfidation epithermal precious
metal mineralization in the crater of Kawah Ijen volcano, Java, Indonesia:
Economic Geology, v. 108, p. 10991118.
Seo, J.H., Guillong, M., and Heinrich, C.A., 2009, The role of sulfur in the
formation of magmatichydrothermal coppergold deposits: Earth and
Planetary Science Letters, v. 282, p. 323328.
Sharman, E.R., 2011, Application of multiple sulfur isotope analysis to
Archean ore-forming processes: Unpublished Ph.D. Thesis, Montral,
Canada, McGill Univesity, 196 p.
Simon, G., Huang, H., Penner-Hahn, J.E., Kesler, S.E., and Kao, L.-S.,
1999, Oxidation state of gold and arsenic in gold-bearing arsenian pyrite:
Ameri- can Mineralogist, v. 84, p. 10711079.
Springer, G., 1969, Compositional variations in enargite and luzonite: Mineralium Deposita, v. 4, p. 7274.
Stefnsson, A., and Seward, T.M., 2004, Gold(I) complexing in aqueous sulphide solutions to 500C at 500 bar: Geochimica et Cosmochimica Acta, v.
68, p. 41214143.
Stoffregen, R.E., 1987, Genesis of acid-sulfate alteration and Au-Cu-Ag
mineralization at Summitville, Colorado: Economic Geology, v. 82, p.
15751591.
Stoffregen, R.E., and Alpers, C.N., 1987, Woodhouseite and svanbergite in
hydrothermal ore deposits: Products of apatite destruction during advanced
argillic alteration: The Canadian Mineralogist, v. 25, p. 201211.
Stoffregen, R.E., and Cygan, G.L., 1990, An experimental study of Na-K
exchange between alunite and aqueous sulfate solutions: The American
Mineralogist, v. 75, p. 209220.
Stoffregen, R.E., Alpers, C.N., and Jambor, J.L., 2000, Alunite-jarosite crystallography, thermodynamics, and geochronology: Reviews in Mineralogy
and Geochemistry, v. 40, p. 453479.

Stone, M., 2010, Sangihe property, Sangihe Island, North Sulawesi, Indonesia: Independent technical report, 130 p.
Taylor, B.E., 2007, Epithermal gold deposits, in Goodfellow, W.D. ed.,
Min- eral deposits of Canada: A synthesis of major deposit-types, district
metal- logeny, the evolution of geological provinces, and exploration
methods: Geological Association of Canada, Mineral Deposits Division,
St. Johns, p. 113139.
Thiersch, P.C., Williams-Jones, A.E., and Clark, J.R., 1997, Epithermal mineralization and ore controls of the Shasta Au-Ag deposit, Toodoggone District, British Columbia, Canada: Mineralium Deposita, v. 32, p. 4457.
Thode, H.G., Monster, J., and Dunford, H.B., 1961, Sulphur isotope geochemistry: Geochimica et Cosmochimica Acta, v. 25, p. 150174.
Thode, H.G., and Rees, C., 1979, Sulphur isotopes in lunar and meteorite
samples: Proceedings of Lunar Planetary Science Conference 10th, Houston, Texas, March 1317, 1979, p. 16291636.
Ulrich, T., Gunther, D., and Heinrich, C.A., 1999, Gold concentrations
of magmatic brines and the metal budget of porphyry copper deposits:
Nature, v. 399, p. 676679.
van Hinsberg, V.J., and Schumacher, J.C., 2007, Intersector element partitioning in tourmaline: A potentially powerful single crystal thermometer:
Contributions to Mineralogy and Petrology, v. 153, p. 289301.
Voudouris, P.C., 2010, Conditions of formation of the Mavrokoryfi highsulfidation epithermal Cu-Ag-Au-Te mineralization (Petrota Graben, NE
Greece): Mineralogy and Petrology, v. 101, p. 97113.
Warren, I., Simmons, S.F., and Mauk, J.L., 2007, Whole-rock geochemical
techniques for evaluating hydrothermal alteration, mass changes, and compositional gradients associated with epithermal Au-Ag mineralization: Economic Geology, v. 102, p. 923948.
White, D., 1957, Thermal waters of volcanic origin: Geological Society of
America Bulletin, v. 68, p. 16371657.
White, N.C., and Hedenquist, J.W., 1990, Epithermal environments and
styles of mineralization: Variations and their causes, and guidelines for
exploration: Journal of Geochemical Exploration, v. 36, p. 445474.
Wilder, A.M., and Seward, T.M., 2002, The adsorption of gold(I)
hydrosulfide complexes by iron sufide surfaces: Geochimica et
Cosmochimica Acta, v.
66, p. 383402.
Williams-Jones, A.E., and Heinrich, C.A., 2005, Vapor transport of metals
and the formation of magmatic-hydrothermal ore deposits: Economic
Geology, v. 100, p. 12871312.
Williams-Jones, A.E., Migdisov, A.A., Archibald, S.A., and Xiao, Z., 2002,
Vapor-transport of ore metals, in Hellmann, R., and Wood, S.A. eds.,
Water- rock interactions, ore deposits, and environmental geochemistry: A
tribute to David A. Crerar: The Geochemical Society, p. 279306.
Williams-Jones, A.E., Bowell, R.J., and Migdisov, A.A., 2009, Gold in solution: Elements, v. 5, p. 281287.
Zezin, D., Migdisov, A.A., and Williams-Jones, A.E., 2011a, PVTx properties of H2O-H2S fluid mixtures at elevated temperature and pressure based
on new experimental data: Geochimica et Cosmochimica Acta, v. 75, p.
54835495.
2011b, The solubility of gold in H2O-H2S vapour at elevated temperature and pressure: Geochimica et Cosmochimica Acta, v. 75, p. 51405153.
Zhang, X., 1993, SULF34: A QUICKBASIC program for calculating sulfur
isotope distribution in log fO2-pH diagram: Computers & Geosciences, v.
19, p. 817823.
Zotov, N., Petrov, K., and Dimitrova-Pankova, M., 1990, Infrared spectra of
Cu (II)-Co (II) mixed hydroxide nitrates: Journal of Physics and Chemistry
of Solids, v. 51, p. 11991205.