Economic Geology

BULLETIN OF THE SOCIETY OF ECONOMIC GEOLOGISTS

VOL. 105 March–April NO. 2

EXPRESS LETTER

SULFOSALT MELTS: EVIDENCE OF HIGH-TEMPERATURE VAPOR TRANSPORT OF METALS

IN THE FORMATION OF HIGH-SULFIDATION LODE GOLD DEPOSITS

JOHN MAVROGENES,1,† RICHARD W. HENLEY,1 AGNES G. REYES,2 AND BYRON BERGER3

1 Research School of Earth Sciences, Australian National University, Canberra, Australia
2 GNS-Science, Lower Hutt, New Zealand
3 U.S. Geological Survey, Denver, Colorado

Abstract
In enargite-gold (high-sulfidation) vein deposits, magmatic fluid is considered responsible for the transport
of metals and sulfur into the depositional regime. New data from Field-Emission SEM analyses of sulfosalt
mineral assemblages (primarily enargite and tennantite) from El Indio, Chile, and Summitville, Colorado, pro-
vide direct evidence of high-temperature deposition, including the following: (1) the preservation of delicate
euhedral quartz assemblages in sulfosalts, (2) a range of discrete Sb-rich sulfosalt, quartz, feldspar, and floura-
patite vug-filling minerals, and (3) symplectic sulfosalt-chalcopyrite textures that are arguably quenched melts.
Together, these features indicate formation from the vapor phase at high temperatures. Furthermore, euhedral
quartz crystals from El Indio contain high-temperature, vapor-rich fluid inclusions. Combined, these observa-
tions are interpreted as suggestive of deposition in response to vapor-phase decompression within fracture
arrays that may be considered the analogues of the feeder fractures beneath large low-grade silver-gold
deposits such as Yanacocha, Peru.

Introduction mineralization evolved from a primary magmatic vapor at

Enargite-gold vein deposits are the analogues of the struc-
turally controlled feeders of shallow, bulk tonnage, high- sul-
fidation deposits such as Yanacocha, Peru. Their geochemical,
fluid inclusion, stable isotope, and geologic data (Rye, 1993;
Einaudi et al., 2003) are consistent with a predominantly
magmatic origin, yet definitive evidence of this connection
has been lacking.
Here we address this problem by careful examination of
sulfide-sulfosalt samples from two archetypal “high-sulfida-
tion” vein deposits: El Indio, Chile, and Summitville, Col-
orado, using Field Emission Scanning Electron Microscopy
(Zeiss Ultraplus FESEM). At El Indio, we focused on sam-
ples of pyrite-enargite-tennantite assemblages (“copper
stage”) that precede the high-grade vein mineralization (Jan-
nas et al., 1999). The very similar geology, paragenetic se-
quences, fluid inclusion temperatures, and stable isotope
compositions of Summitville have recently been summarized
by Bethke et al. (2005) who, based on stable isotope system-
atics, argue that the fluid phase responsible for alteration and
† Corresponding author: john.mavrogenes@anu.edu.au
©2010 by Economic Geology, Vol. 105, pp. 257–262
0361-0128/10/3871/000-6
780°C or higher.
Observations
We here present data for polished sections and fresh fracture
surfaces of sulfosalt samples from El Indio and Summitville
that form part of an on-going examination of sulfide and sul-
fosalt textures and compositions from enargite-gold vein de-
posits from around the world. Annotated photomicrograph and
SEM images (Figs. 1–3) illustrate the paragenetic similarities
between these two otherwise unrelated deposits. Figure 1
shows euhedral quartz crystals within sulfosalt assemblages
that occupy voids and cracks within earlier fractured and cor-
roded pyrite. Pristine euhedral quartz crystals (Fig. 1a) are
commonly seen “floating” in sulfosalt, and also as delicate den-
dritic clusters of crystals penetrating the surrounding sulfosalt.
In some cases the quartz is corroded and infilled by sulfosalt
(Fig. 1b). Sulfosalt textures (Fig. 2) are both texturally and
chemically (variations in As:Sb:Fe) extremely heterogeneous
and contain discrete domains of symplectic intergrowths (Fig.
2b, c) similar to those seen in quenched experimental sulfide
melts (Fig. 2d) juxtaposed with single phase domains. The sul-
fosalt assemblages are riddled with cavities (Fig. 3), which
Submitted: November 20, 2009
257 Accepted: January 4, 2010
258 EXPRESS LETTER

a b

20 µm EI1300 100 µm EI4216

c d

100 µm EI1300 100 µm SMTV

FIG. 1. Quartz-sulfosalt assemblages from El Indio and Summitville: a. panoramic photomicrograph montage of an Fe
tennantite (Fe ~ at. 6%) pocket in fractured and corroded pyrite containing euhedral quartz crystals. b. Photomicrograph of
resorbed quartz in Fe tennantite. c. FESEM backscattered electron image of euhedral quartz in heterogeneous and locally
zoned Fe tennantite. The bright areas are richer in Sb, whereas darker areas are richer in As. d. Photomicrograph of euhe-
dral quartz “dendrite” in enargite. (Sample details: El Indio enargite veins - EI1285 = DDH1285, 31.1m; EI1300 = DDH
1300, 490.5m, EI 4216 = DDH4216, 27.7m, and Summitville veins - SMTV - Underground sample USGS87JG-EN-VS
(kindly provided by Dr. John Gray, USGS, Denver). Other abbreviations listed in Figure 2 caption.

Sb-Fe-Tn

z
a Py b Py
Fe-Tn
z

c
Ccp

Cavities c
30 µm EI1285 10 µm EI1285

c Fe-Tn d
Ccp

10 µm EI1285 100 µm

Fig. 2. Sulfosalt textures from El Indio: a. Photomicrograph of fine blebs of chalcopyrite within Fe tennantite surround-
ing corroded pyrite. b. FESEM BSE image the same area as in (a) with localized As-Sb zonation and symplectic inter-
growths. c. Close-up of b showing symplectic intergrowths resembling quenched experimental melt (d). The location of area
c is shown in Fig. 2a, b. (Abbreviations: Ccp = chalcopyrite, En = enargite, Fap = fluorapatite, Fe-Tn = iron-bearing arsenic-
rich tennantite, Qz = quartz, Py = pyrite, Sb-Tn = tennantite with relatively high Sb/As ratio).

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 EXPRESS LETTER 259

a Cu Si b
Al En

Sb-Tn

20 µm SMTV 300 nm SMTV

c d
KAlSi

En
Sb
1 µm SMTV 200 µm

e f
Fap
Fe-Tn

Qz

Fe-Tn

100 µm EI1300 20 µm EI1300

g h Fe-Tn
Fe-Tn

En

Sb

200 nm EI1300 100 µm EI1300

FIG. 3. Crystal-lined vugs in sulfosalt assemblages: a. FESEM secondary electron image of a cleavage fragment of Sum-
mitville enargite; note the abundance of small vugs and the wide range of discrete minerals existing in cavities; the inset
shows a beehive-shaped outgrowth containing Cu (?CuS), fibrous Si (?SiO2), and acicular Al (Al-silicate?). b. Close-up of
area (a), showing very small tetrahedral crystals of Sb-rich sulfosalt (luzonite?) in a cavity in the enargite. c. Close-up from
a of a cavity containing K-feldspar and growths of an Sb-rich phase (?luzonite). d. a FESEM SE image of an experimental
charge of quenched vapor-rich vesicular enargite and halos of tennantite around the cavities. Images e-h are FESEM SE
images of a cleavage fragment of El Indio Fe tennantite showing void spaces containing (e) crystalline quartz, (f) euhedral
fluorapatite crystals, (g) an Sb-rich phase with similar growth form to c, and (h) enargite, all growing from the internal wall
of the cavities.

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260 EXPRESS LETTER
appear as subspherical vugs (Fig. 3b, c) or as more regular in-
terstitial domains between crystalline material (Fig. 3e-f). Both
cavity types contain minerals, either as crystal linings of Sb-rich
sulfosalts (Fig. 3f), or as discrete crystalline K-Al silicate (pre-
sumably K-feldspar), aluminosilicates, fluorapatite, or quartz.
The vugs presented here appear analogous to miarolitic cavities
in granitic pegmatites.
Interpretation
The coexistence of distinct textural domains (some of which
preserve quenched melt textures (Mavrogenes et al., 2001;
Tomkins et al., 2004)), delicate euhedral quartz crystals and
clusters (Fig. 1d), and crystal-lined vugs indicate formation
from a vapor-saturated Fe-Cu-As-Sb-S (± Pb, Zn, Si, P, Ca, K,
Al) melt. In neither deposit is there evidence of any high-tem-
perature thermal event postdating the sulfide-sulfosalt as-
semblages that could otherwise account for the formation of
these textural relationships.
Figure 4 shows the chemistry of the El Indio and Sum-
mitville sulfosalt assemblages in relation to the melt field of
the system Cu-As-Fe-S between 600° and 665.5°C (Maske
and Skinner, 1971; Tomkins et al., 2004). The symplectic
phase compositions (Fig. 4) are consistent with trapping of
melt of near-Fe-tennantite composition and containing up to
about 5 at. percent Sb with subsequent heterogeneous solid-
ification and crystallization to form the distinct compositional
and textural domains (Fig. 2a, c) as a consequence of differ-
ential rates of diffusive heat transfer within the cooling as-
semblage. Our observation that cavity-lining sulfosalts are en-
riched in Sb relative to their hosts is compatible with a simple
binary melt + vapor system fractionating between endmem-
ber enargite (m.p. 682°C) and famatinite (m.p. 627°C) where
iron up to a few percent does not significantly affect phase be-
havior. This interpretation is compatible with the analytical
data in Figure 4 in which melt compositions retreat from the
Cu-rich compositions to As (± Sb)-enriched compositions
with decreasing temperature. Subsolidus crystallization of
the matrix surrounding inclusions results in a heterogeneous
S Fe Legend
zz - Figure 2b
Figure 2c
Mineral end-members
Ccp
En
MELT
Ccp, ISS
Fe-Tn 600°C Melt
665.5°C Melt
Figure 2c
Figure 2b, z-z
Bn
Cu As
Fe-Tn
As En Cu
FIG. 4. a. Quantitative analyses of Fe tennantite compositional variation
within the areas shown in Fig. 2b and c in relation to endmember mineral
compositions, and b. The melt field for Cu-As-S at 650°C derived experi-
mentally by Maske and Skinner (1971). Abbreviations as above and Bn = bor-
nite, ISS = intermediate solid solution, Lz = luzonite.
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sulfosalt assemblage made up of chemically distinct domains
(Fig. 2b), characterized by symplectic intergowths or that dif-
fer primarily in the frequency of inclusion of microcavities.
Systematic zonation patterns adjacent to pyrite contacts (Fig.
2b) or around euhedral quartz (Fig. 1c) have a distinct chem-
ical trend that is most likely due to postcrystallization diffu-
sion-controlled reaction with vapor flowing through con-
nected cavities or “tubules.” The subsolidus unmixing of
Cu-Fe-As–Sb-S compositions below about 620°C to form dis-
ordered layered sequences and polytypes are summarized by
Posfai and Buseck (1998) for the simpler enargite-luzonite-
famatinite system. At El Indio, we also observe intergrowth of
enargite and Fe tennantite as did Jannas (1995). It is worth
noting that Lewis (1956, fig. 8) reported “eutectic” textures at
Quiruvilca, Peru, that are remarkably similar to those pre-
sented here.
Figure 3e suggests that some quartz growth occurred
within vugs during solidification of the primary sulfosalt melt,
indicating, as do the other discrete phases observed, open-
system cooling of the assemblage with vapor flow through a
connected array of tubules that subsequently neck to form
the crystal-lined cavities. We interpret that the textures
shown in Figure 2 are indicative of quartz deposition during
the development of the sulfosalt assemblages. The strong
nonlinearity and asymmetry of compositional banding away
from the euhedral quartz (Fig. 1c) is a consequence of the
mutual interference of thermal and compositional gradients
controlling diffusion around tubules as vapor flow continues
during subsolidus crystallization. The perfect hexagonal mor-
phology of quartz crystals in these samples suggests but does
not confirm formation temperatures in the β-quartz field
(above 575°C).
The euhedral quartz crystals contain abundant very small
fluid inclusions that appear empty (Fig. 5), consistent with
trapping of a very low density vapor with only a few larger
two-phase inclusions. Preliminary heating experiments on
some of these vapor-rich fluid inclusions yield temperatures
of 455°C (Fig. 5b), and other inclusions show complex ho-
mogenization-decrepitation behavior above 500°C.
The pre-sulfosalt pyrite occurs on the walls of dilatational
spaces within the evolving vein and is likely to have formed
directly from the vapor phase below its upper stability limit of
742°C. It was subsequently fractured, infilled and strongly
corroded where in contact with the sulfosalt melt.
Discussion
We propose that these three new types of observational
data for the “copper stage” assemblages at El Indio and Sum-
mitville are consistent with a hypothesis involving solidifica-
tion of a sulfosalt melt that condensed from a vapor phase at
near-magmatic temperatures. We specifically do not here ad-
dress the later, arguably lower temperature, gold and silver
stages of these deposits (e.g., Jannas et al., 1999).
This hypothesis is consistent with the geologic and stable
isotope data from these deposits and the models proposed by
Jannas et al. (1999) and Bethke et al. (2005). These authors
showed that during their formation after the advanced argillic
alteration stage, the El Indio and Summitville vein deposits
were open to and formed well within 1.5 km of the paleosur-
face so that the maximum fluid pressure for mineralization is
260
 EXPRESS LETTER 261

400
a)
Throttled
magmatic
vapor

LH
0.02
300

rve V

5wt
on cu

%
Pressure bars

rati
Liquid +Vapor

Satu
Halite-
saturated Condensation of
200 vapor sulfosalt melt

0.01w
and
vapor-streaming

t%
0.0
05w

5wt %
100

t
%

sio c
es ati

1wt %
n
pr b
m dia

0.1wt %
co -a
de asi
Qu
0
200 400 600 800
Temperature °C
b)
FIG. 6. Rapid decrease in the solubility of halite in the vapor phase in the
system NaCl-H2O (adapted from Sourirajan and Kennedy, 1962). Quasi-isen-
thalpic decompression of a magmatic vapor from 375 bars to less than 150
bars results in condensation of a sulfosalt melt and deposition of quartz, sul-
fosalts, aluminosilicates, and fluorapatite in tubules through the melt as gas
streaming and chemical exchange continue.

TH,V
455oC
FIG. 5. Photomicrograph of a doubly polished euhedral quartz crystal
from El Indio (EI1300) showing (a) primary fluid inclusions along growth
planes, and (b) a vapor-rich inclusion that yielded a homogenization temper-
ature (Th to the vapor phase) of 455°C. Vugs highlighting growth zones also
contain sulfosalts, confirming the coincidence of quartz growth and sulfosalt
melt deposition. Scale bars = 50 microns.
150 bars, assuming that an external groundwater system con-
strains vapor expansion. The lithostatic pressure at the base of
a vein array at 1.5 km would be about 375 bars, representing
the minimum pressure of a single phase vapor or gas expand-
ing through a magmatic vapor reservoir beneath the deposit.
At the base of the array the magmatic vapor is throttled to ap-
proximately 150 bars with further expansion. The high-tem-
perature conditions (>600°C) suggested by the recognition of
high-temperature sulfosalt assemblages confirm that at these
low flow pressures the fluid phase had the properties of a gas
(or “vapor”).
The principal process controlling melt condensation and
the deposition of discrete sulfosalt crystals, aluminosilicates,
apatite, and quartz is expansion of the vapor phase with rela-
tively low loss of heat to surroundings. Figure 6 shows the
rapid decrease in halite solubility in the vapor phase of the
simple NaCl-H2O system as initially halite-undersaturated
magmatic vapor expands within a fracture array open to the
surface. The systematics of such magmatic vapor phase ex-
pansion in a near-surface fracture array are described in a
separate contribution. The expansion of magmatic vapor to
pressures of only a few tens of bars results in very low vapor
densities and, since the solubilities of many components
under these conditions are a function of vapor density, expan-
sion leads to immediate super-saturation and rapid mineral
deposition or melt condensation (Fig. 7). For example, the
solubility of silica in water as a gas phase is strongly depen-
dent on vapor density (Morey and Hesselgesser, 1951).
Therefore, pressure decrease results in the formation of eu-
hedral quartz in vapor flowing through connected tubules
within the melt and, through density contrast, the distribution
of quartz euhedra in low viscosity higher density, sulfosalt
melt (Fig. 1a). The solubility of sulfide minerals is also pres-
sure dependent because solvated species destabilize (Pokrovski
et al., 2008) during expansion. In turn, this view enables us to
identify the formation of high-sulfidation copper-gold de-
posits with common volcanic phenomena such as fumaroles
and solfataras in active volcanoes.
These new data therefore provide an integrated picture of
the way vapor expanding from shallow composite intrusive
systems first deposits Cu-Fe-As-Sb-S assemblages to form
high-grade veins. Subsequent expansion of this depleted
vapor phase or mixing with contemporary groundwater sys-
tems results in the later silver-gold stages and, near surface,
the formation of low-grade bulk tonnage copper-gold de-
posits. This vapor-expansion hypothesis also allows reconcili-
ation between published vapor homogenization temperatures

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262
Groudwater
~1000 bars Silica+alunite
alteration
500 - 700 °C
Pressure
id
Gas
Liqu
Phase separation
B’ B 0.05
C Indio district, Chile: Unpublished Ph.D. dissertation, Cambridge, Massa-
Halite + Vapor
D dation deposit types in the El Indio district, Chile: Society of Economic
0 Low-grade Cu-Au, Fumaroles
solfatara, crater lakes
Enthalpy
FIG. 7. Simplified schematic of the vapor expansion model for the forma-
tion of enargite-gold vein deposits. Magmatic vapor is throttled from lithosta-
tic pressure in the magmatic reservoir (~300 bars) to low pressure (~150 bars)
in fracture systems at depths of at most 1.5 km. The approximate density of
the vapor phase (ρ, kg m–3) is shown. The early alunite-silica-pyrite stage is a
consequence of heat loss during depressurization (path ABB') from a mag-
matic vapor containing a few percent NaCl equiv into the 2-phase field of the
system NaCl-H2O to form acidic condensate (B') and condensate-groundwa-
ter mixtures. Expansion paths (AC) with lower heat loss through subsequent
brittle fractures remain in the vapor field or pass into the vapor and halite field
of the system (Fig. 5) with immediate deposition of sulfides, sulfosalts, and a
range of minor phases (Fig. 3) including quartz (Fig. 1). The metal-depleted
vapor phase expands and discharges at the surface (D) with major heat loss oc-
curring due to groundwater mixing and vapor loss, and consequent surface
emissions such as solfatara, fumaroles and low grade copper-gold-silver min-
eralization associated with large zones of advanced argillic alteration.
over 500°C (e.g., Ruggieri, 1997; Wang et al.; 1999, Bethke et
al., 2005), with the plethora of lower temperature fluid inclu-
sion data from quartz, alunite, and enargite in the bulk ton-
nage type deposits.
Acknowledgments
We thank Carlos Tellez and François Robert (Barrick Gold
Corporation) for providing the sample suite from El Indio,
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EXPRESS LETTER
and Frank Brink (Australian National University) for guid-
ρ = 0.3
ance in the FESEM analyses. We also thank Andy Tomkins,
Al Hofstra, and Klaus Schulz for constructive reviews.
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