Economic Geology

Vol. 98, 2003, pp. 147–156

Formation of Anhydrous and Hydrous Skarn in

Cu-Au Ore Deposits by Magmatic Fluids
L. D. MEINERT,†,*
Department of Geology, Washington State University, Pullman, Washington 99164-2812

J. W. HEDENQUIST,
Department of Geology and Geological Engineering, Colorado School of Mines, Golden, Colorado 80401-1887

H. SATOH,
Geological Survey of Japan, AIST Tsukuba Central 7, 1-1-1 Higashi, Tsukuba 305-8567, Japan

AND Y. MATSUHISA
Geological Survey of Japan, AIST Tsukuba Central 7, 1-1-1 Higashi, Tsukuba 305-8567, Japan

Abstract
Most skarn ore deposits are characterized by two distinctly different alteration styles. An early prograde stage
with anhydrous minerals, such as garnet and pyroxene, forms from relatively high-temperature, hypersaline liq-
uid. A later retrograde stage with hydrous minerals, such as epidote, amphibole, and chlorite plus sulfide ore
minerals, forms from lower temperature, lower salinity fluids. These two alteration stages commonly have been
thought to reflect a dominance of magmatic and meteoric water, respectively, with relevance to the source of
ore metals. We report data from two different skarn systems, one being part of the world’s largest Cu-Au re-
source. Stable isotope compositions of anhydrous and hydrous alteration minerals from both deposits indicate
a magmatic source for both the prograde and retrograde stages: δ18O averages 5.0 per mil for garnet (range,
3.4–7.2‰), 6.5 per mil for pyroxene (4.3–8.2‰), and 7.1 per mil for amphibole (4.3–8.7‰). The δD values of
late amphibole are more complex, with magmatic values (–77 to –78‰) for one deposit and both magmatic
and lighter values for another deposit that could be explained either by magmatic degassing or by limited mix-
ing with meteoric water. We conclude that the differences in fluid composition—prograde versus retrograde
stages—resulted from a magmatic fluid that intersected its solvus during the early stage, creating vapor and hy-
persaline liquid, whereas in the later stage this magmatic fluid did not intersect its solvus because it followed
a different cooling path. This late, low- salinity liquid only boiled once its vapor-pressure curve was reached,
causing sulfide ore to precipitate during the retrograde stage.

Introduction of magmatic and meteoric water, respectively (Einaudi et al.,

THE SOURCE of ore fluids is one of the most important topics
of applied geologic research (Hedenquist and Lowenstern,
1994; Pettke and Diamond, 1997; Harris and Golding, 2002).
Many studies have demonstrated multiple sources of fluids re-
sponsible for forming ore deposits. A variety of theories of ore
genesis invoke interactions among such fluids, particularly
those of magmatic and meteoric origin (Giggenbach, 1997;
and Taylor, 1997, respectively). Since most skarn ores have an
intimate spatial relationship with magmatic intrusions, their
minerals should provide a clear record of the fluid(s) that were
present in the intrusive environment during ore formation.
Skarn ore deposits are typically characterized by two distinct
alteration styles: an early prograde stage with anhydrous min-
erals, such as garnet and pyroxene, which forms from rela-
tively high-temperature, hypersaline liquid (Kwak, 1986); and
a later retrograde stage which consists of hydrous minerals,
such as epidote, amphibole, and chlorite, and forms from lower
temperature, lower salinity fluids (Kwak, 1986). These two al-
teration stages commonly are thought to reflect a dominance
†Corresponding
author: e-mail, meinert@wsu.edu
*Address after August 1, 2003: Department of Geology, Smith College,
Northampton, MA 01063; e-mail, Lmeinert@smith.edu.
1981). A review of stable isotope systematics in skarn systems
by Bowman (1998) indicates a dominance of magmatic waters
during the early prograde stage, in which anhydrous minerals
dominate, and a range from largely magmatic to largely mete-
oric waters during the later retrograde stage in which hydrous
minerals dominate.
We present data from two copper skarn deposits in Irian
Jaya and Canada of different ages, host rocks, and geologic
terrane. In both deposits, there was a transition from high-
temperature, hypersaline liquid associated with prograde gar-
net-pyroxene skarn to lower temperature, lower salinity liquid
associated with retrograde skarn alteration. Based upon data
presented here, we interpret this transition to have been
caused by a common parent magmatic fluid that experienced
a change in pressure-temperature path during ascent.
Big Gossan Deposit, Ertsberg District, Irian Jaya
The Ertsberg district contains multiple Cu-Au skarn and
porphyry deposits, including the original Ertsberg discovery,
the GBT/IOZ/DOZ orebodies, Dom, Big Gossan, Kucing
Liar, and the largest of all, Grasberg, plus several other min-
eral occurrences in various stages of exploration and develop-
ment (Fig. 1). Individually, Grasberg is the largest gold mine

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148 MEINERT ET AL.

Ertsberg District
50° Papua
New
70° Guinea
Ti
45°
Irian Jaya Tk
Pacific
Ocean
Ti 25°Cairns
Lembah Tk
Grasberg
Tembaga Australia

* Kkel
Sydney

* Tw

Yello 70°
Kucing w Va
lley S
* Liar
GBT
yncli
ne

S4° Fig. 2A *
Ertsberg 45° Puncak

Big Gossan * * Jaya

4883m

*
Dom
70°

Intrusion (Ti)
Thrust fault
Tertiary
Fig. 2B 40°
75°
carbonate rocks
Cretaceous
clastic rocks
60°
0 km 2 E137°

FIG. 1. Location and geology of the Ertsberg district, Irian Jaya, showing major deposits and location of cross sections of
Figure 2 (modified from Meinert et al., 1997).

and the third largest copper mine in the world. The deposits
of the Ertsberg district collectively constitute the world’s
largest Cu-Au resource. At the end of 2001, proven and prob-
able reserves were estimated at 2,600 Mt of ore at an average
grade of 1.13 percent Cu, 1.05 g/t Au, and 3.72 g/t Ag, con-
taining 23.8 Mt of recoverable copper, 64.5 Moz of recover-
able gold, and 151.6 Moz of recoverable silver (Freeport Mc-
MoRan Annual Report, 2001).
The Big Gossan Cu-Au skarn deposit is the highest grade
copper deposit in the Ertsberg district, with current reserves
of 37.4 Mt grading 2.69 percent Cu, 1.02 g/t Au, and 16 g/t Ag
(Meinert et al., 1997). Ore is associated with a series of 3 to 4
m.y. granodioritic dikes (McMahon, 1994 a, b, c) that have in-
truded close to the near-vertical faulted contact between the
Shale Member of the Cretaceous Ekmai Formation and the
stratigraphically overlying carbonate sequences of the Pale-
ocene Waripi and Eocene Faumai Formations. Most miner-
alized and altered sequences occur in the purer carbonate
rocks of the Waripi Formation, although biotite and calc-sili-
cate hornfels alteration also occur in the clastic footwall rocks
adjacent to skarn ore. The scale of the Big Gossan skarn sys-
tem is more than 1 km along strike, more than 500 m verti-
cally (open at depth), and up to 200 m in width for an aggre-
gate volume of more than 0.1 km3 (Fig. 2).
The calcic ± magnesian skarn assemblage in the Waripi For-
mation hosts the bulk of the Big Gossan orebody and is char-
acterized by relatively coarse-grained garnet and pyroxene,
with an average mineral ratio of about 1:2. The average com-
position of all analyzed garnets is andradite84.7grossular-
ite13.5spessartine1.5pyrope0.3. Garnet higher in the deposit and
on the western and eastern margins shows a slight increase in
iron relative to that in deeper, more central locations. The
iron content of pyroxene is zoned in both space and time. The
pale, proximal, and early pyroxene is nearly pure diopside
(Di) and the dark green, distal, and late pyroxene ranges up
to 75 mole percent hedenbergite (Hd) with minor jo-
hannsenite (Jo). In agreement with general skarn zonation
patterns (Meinert, 1992, 1997), pyroxene becomes more iron-
and manganese-rich toward the margins of the known de-
posit, suggesting that the hydrothermal system was centered
in the middle of the deposit, coincident with the largest mass
of dike. A similar zonation occurs vertically; the average py-
roxene composition for the highest third of the skarn system
is Di58Hd38Jo4, whereas the average for the deepest third is
Di86Hd13Jo1.
Amphibole in the Big Gossan skarn system ranges from
actinolite to cummingtonite, with the main substitution being
Fe-Mg-Mn for Ca. Most amphibole occurs as an alteration
product of pyroxene, typically with quartz, carbonate, anhy-
drite, and sulfides. Subcalcic amphiboles occur on the mar-
gins of skarn where pyroxene has been totally replaced. In
these occurrences, amphibole is intimately intergrown with
quartz and carbonate, the latter ranging in composition from
calcite to manganiferous siderite, suggesting that the location

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 FORMATION OF Cu-Au SKARN BY MAGMATIC FLUIDS
SW NE SW
BGU 14-2
BGU 14-3
BGU 14-6
BGU 14-7
A B
FIG. 2. Cross sections through the Big Gossan skarn system showing the distribution of garnet and pyroxene skarn. Lo-
cations shown in Figure 1.
of the pyroxene-amphibole transition was affected by higher
XCO2 near the marble front (Meinert et al., 1997). Thus, at a
given temperature near the skarn-marble contact, pyroxene
was altered to amphibole plus carbonate according to a reac-
tion (based upon measured compositions) such as: pyroxene
+ H2O + CO2 = subcalcic amphibole + quartz + carbonate—
7Ca(Fe0.5Mg0.4Mn0.1)Si2O6 + H2O + 7CO2 = Ca(Fe2.8 Mg2.6
Mn0.6)Si8O22 (OH)2 + 6SiO2 + 7(Ca0.86Fe0.1 Mg0.03Mn0.01)CO3.
Marble occurs for tens to hundreds of meters beyond the
Big Gossan skarn in the Waripi Formation hanging wall.
Within this aureole, grain size decreases systematically away
from skarn and dike contacts. Numerous planar to wavy vein-
lets, usually less than 1 mm thick and oriented perpendicular
to the skarn front, appear to represent paleofluid conduits.
The dark centerline of these veinlets is marked by a concen-
tration of carbon, pyrite, sphalerite, galena, chlorite, serpen-
tine, and/or clay.
The fluid associated with prograde skarn at Big Gossan is a
high-temperature NaCl-KCl hypersaline liquid with a low
CO2 content, <0.05 mole percent (Meinert et al., 1997). Ho-
mogenization temperatures for fluid inclusions in pyroxene
range from 320° to 485°C, average 410°C, and formed at a
pressure of 50 MPa, equivalent to a depth of 2 km, under
lithostatic conditions. Most fluid inclusions in pyroxene
contain multiple daughter minerals including halite, sylvite,
chalcopyrite, hematite, and anhydrite, indicating that a com-
plex brine was present (Fig. 3A, B). Total salinity ranges from
38 to 65 wt percent NaCl + KCl; mean salinities are 22 wt
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149
NE Elev. (m)
BGU 10-1
2900
Ertsberg Intrusion
BGU 10-3
Intrusive Breccia
2800
Massive sulfide cap
Pyx > Gar skarn
2700
Gar > Pyx skarn
Big Gossan dikes
2600
Marble (Tw)
Kkeh marker shale
BGU 10-5
Kembelangan Group
2500
BGU 10-6
2400
percent KCl and 35 wt percent NaCl. By contrast, fluid in-
clusions in quartz and anhydrite associated with retrograde al-
teration average 7.1 wt percent NaCl equiv and spatially as-
sociated fluid inclusions homogenize to liquid and vapor at
370° to 380°C (Fig. 3C, D ). This corresponds to boiling at a
pressure of 20 MPa, equivalent to a depth of 2 km below the
paleowater table under hydrostatic conditions. Since these
samples came from 600 m beneath the present surface, the
data indicate that at least 1.4 km of erosion has occurred in
the Ertsberg district over the past 4 m.y.
Mines Gaspé, Quebec
Like the Ertsberg district, Mines Gaspé in Quebec has both
porphyry and skarn ore (Fig. 4); however, the Devonian host
rocks and porphyritic quartz monzonite stocks have U-Pb zir-
con ages of 385 ± 2.6 Ma (Stephenson et al., 1998), which is
much older than the ages at Ertsberg. The Mines Gaspé dis-
trict was discovered in 1921 and has produced more than 150
Mt of ore averaging 0.9 percent Cu (with production grades
up to 3.4% Cu). It has new drilled resources at Porphyry
Mountain of 200 Mt grading 0.73 percent Cu and 0.08 per-
cent Mo (Hussey and Bernard, 1998). The scale of the Por-
phyry Mountain skarn system is more than 1 km in diameter
and more than 800 m vertically (open at depth) for an aggre-
gate volume of more than 0.8 km3 (Fig. 5).
The Devonian host rocks at Mines Gaspé have been gently
folded and consist of carbonaceous silty limestone, calcareous
149
150 MEINERT ET AL.

FIG. 3. Photomicrographs of inclusions in skarn minerals. A. Multiphase fluid inclusion in pyroxene containing vapor
bubble (V), halite (H), sylvite (S), hematite? (Hm), and unknown mineral (X). B. Multiphase fluid inclusion in pyroxene
containing vapor bubble (V), halite (H), sylvite (S), and chalcopyrite (Cpy). C. Vapor-rich fluid inclusion in quartz. D. Part
of a large pyroxene crystal which has been completely altered to amphibole (amph) and anhydrite. The anhydrite contains
hundreds of vapor-rich fluid inclusions, most of which homogenize to vapor.

Quebec
Mines York River Fm.
Gaspe Porphyry Brook
e
nclin
ampau Sy
Ch
Maine
Porphyry A
Atlantic Mtn
Boston Ocean
920A Indian Cove Fm. 20°

890 923 900

905 886
1 km 793 904 909

Copper
Mtn A' N65°

Shiphead Fm. Murdochville

15°

metamorphic aureole Forillon Fm.

(limit of bleaching) E65°30‘

FIG. 4. Location and geology of the Mines Gaspé district (modified from Allcock, 1982). Crosshatched areas are surface
projections of porphyry plutons. Sample locations are surface projections of drill holes.

siltstone and shale, and minor marker tuff beds of the Foril-
lon, Shiphead, and Indian Cove Formations (Gower and
Walker, 1993). These units were intruded by the Copper
Mountain stock and the Porphyry Mountain stock, the latter
encountered only in drill core. The margins of both stocks are
irregular, with numerous small dikes and sills intruded along
bedding planes. Both stocks have been intensely altered by
the addition of secondary K feldspar and biotite, with rela-
tively minor and late quartz-sericite-pyrite.
Close to the Porphyry Mountain intrusion, argillaceous
limestone was altered to coarse-grained, dark reddish-brown
skarn, consisting of >90 vol percent garnet, whereas more

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 FORMATION OF Cu-Au SKARN BY MAGMATIC FLUIDS
A'
Sea
Level
-500 m
Cu
Mo
-1000 m
FIG. 5. Cross section with no vertical exaggeration through the Porphyry Mountain skarn system showing the distribution
of garnet and pyroxene skarn. Location (A’–A) shown in Figure 4. Top of cross section (sea level) is about 900 m below the
surface of Porphyry Mountain. Arrows indicate direction of increasing Cu and Mo grades relative to K silicate-altered core
of the intrusion. Gar = garnet, Pyx = pyroxene.
clastic-rich units were altered to dark- green pyroxene horn-
fels. With increasing distance from the intrusion, skarn in
limestone becomes more pyroxene rich and the calc-silicate
hornfels in more clastic-rich units becomes lighter in color.
All skarn was overprinted by veinlets and vein envelopes of
hydrous minerals such as amphibole, chlorite, and epidote,
usually associated with sulfide minerals. Surrounding the two
main mineralized stocks is a composite aureole of bleaching
and recrystallization marked by a relatively sharp transition
from recrystallized white marble to fine-grained, dark-gray
limestone about 10 to 200 m beyond the limit of skarn (Fig.
4). The distal thermal aureole can be detected for several
kilometers beyond visible alteration by a very subtle change in
illite crystallinity (Williams-Jones, 1986).
Previous fluid inclusion and stable isotope investigations of
the Copper Mountain porphyry copper deposit at Mines
Gaspé did not distinguish prograde and retrograde alteration
stages but did find evidence for a predominance of magmatic
fluid, except for a relatively late, postmineralization influx of
meteoric water. The proximal porphyry ore at Copper Moun-
tain formed from a fluid largely of magmatic origin (δDH2O =
–42 to –61‰, based on extraction of inclusion fluids; Shelton,
1983). Fluid inclusion results for skarn (Shelton, 1983)
indicate high temperatures (TH = 334°–506°C) and high
salinities (15–56 wt % NaCl equiv), similar overall to the val-
ues reported from the prograde stage of the Big Gossan cop-
per skarn.
Stable Isotope Results
Recent advances in stable isotope analytical methods allow
analysis of considerably smaller samples (a few mg for laser
fluorination lines) than is required for conventional analyses
(tens to hundreds of mg). This is particularly important for
studies of skarn systems due to the finely intergrown na-
ture of most skarn minerals and the complex reactions that
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151
A Gar >> pyx skarn
Pyx > gar skarn
Indian Cove Fm.
Fault subparallel to Dark green pyx
Porphyry Brook
Fault Zone
Light green pyx
Calc-silicate hornfels
Hornfels
Forillon Fm. Shiphead Fm.
Marble
Biotite hornfels
Quartz monzonite
porphyry
Limit of intense
K-silicate alteration
commonly result in incomplete replacement of one phase by
another (e.g., Shimazaki and Kusakabe, 1990).
The determination of δ18 O (VSMOW) compositions by
laser fluorination of 2- to 3-mg samples from Big Gossan
(Table 1) provided average values of 6.1 per mil for garnet
(range, 5.5–7.2‰), 7.4 per mil for pyroxene (7.0–8.2‰), and
8.6 per mil for amphibole (8.6–8.7‰), excluding one sample
with calcite inclusions that caused slightly higher δ18 O values
(10.9–11.1‰). No systematic spatial variation in isotopic
compositions was determined for any of the mineral species.
There is an average pyroxene-garnet difference of 1.3 per mil.
If this difference reflects a bulk equilibrium signature of the
system, a calculated fractionation temperature (Zheng, 1993)
would be 370° ± 70°C (Table 1). This is in general agreement
with measured fluid inclusion temperatures, with all but one
value ranging from 400° to 455°C (Table 1). Conventional
analysis of δD via Zn reduction of 100- to 200-mg samples of
amphibole resulted in average values of –77.5 per mil (range,
–77 to –78‰); no lower values were detected.
For Mines Gaspé samples (Table 1), the δ18O values aver-
age 4.2 per mil for garnet (3.4–5.6‰), 5.3 per mil for pyrox-
ene (4.3–6.0‰), and 4.9 per mil for amphibole (4.3–5.2‰).
Again, if the average pyroxene-garnet difference of 1.1 per
mil reflects a bulk equilibrium signature of the system, the
calculated fractionation temperature is 450° ± 100°C, also in
general agreement with independent temperature estimates
of 450° to 500°C and slightly higher than the temperature es-
timates for Big Gossan. The δD value of primary igneous am-
phibole at Mines Gaspé is –87 per mil, whereas skarn amphi-
bole record values from –78 per mil through –115 to –143 per
mil.
Discussion
Unlike contact metamorphism that is the result of the in-
trusion of relatively dry magmas (cf. Valley, 1986), world-class
151
152 MEINERT ET AL.

TABLE 1. Stable Isotope and Temperature Data for the Big Gossan and Mines Gaspé Skarn Deposits

Big Gossan

Measured Calculated Measured Calculated Measured Flinc

Sample no. Mineral δ18O(VSMOW) δ18Ofluid δD(SMOW) δDfluid H2O T
(‰) (‰) (‰) (‰) (wt %) (°C)

1-6-600 Actinolite 8.6 9.6 –78 –24 2.6 350

1-6-600 Actinolite, duplicate 8.6 9.6
1-6-600 Actinolite, duplicate 8.7 9.7 350
8-1-213 Actinolite# 11.1 12.1 –77 –23 1.9 350
8-1-213 Actinolite #, duplicate 10.9 11.9 350

9-5-340 Pyroxene 7.0 8.8 455

10-3-78 Pyroxene 7.0 8.7 445
23-2-122 Pyroxene 7.3 9.0 445
23-4-420 Pyroxene 7.5 9.2 445
14-6-400 Pyroxene 8.2 10.1 490

26-4-250 Garnet 5.5 8.1 400

14-6-491 Garnet 5.6 8.2 400
23-2-165 Garnet 5.7 8.3 400
9-5-465 Garnet 6.2 8.8 400
8-5-187 Garnet 7.2 9.8 400
∆pyx-gar = 1.3 370 ± 70

Gaspé

Porphyry Mtn Hornblende 5.0 7.4 –87 –70 2.5 700

923-4859 Hornblende 4.3 5.3 –78 –24 1.8 350
900-5660-1 Actinolite 5.2 6.2 –115 –61 1.6 350
900-5660-2 Actinolite 5.2 6.2 –143 –89 1.6 350
900-5660-2 Actinolite* 4.9 5.9 350
793-2990 Actinolite 5.0 6.0 –130 –76 1.8 350

923-5008 Pyroxene 4.3 6.2 500

904-4011 Pyroxene 5.4 7.3 500
904-4011 Pyroxene, duplicate 5.6 7.5 500
890-4085 Pyroxene 6.0 7.9 500

909-4245B Garnet 3.4 6.2 450

905-3210 Garnet 3.6 6.4 450
904-3995 Garnet 3.6 6.4 450
886-4351 Garnet 4.3 7.1 450
920-5012 Garnet 4.5 7.3 450
909-4245A Garnet 5.6 8.4 450
∆pyx-gar = 1.1 450 ± 100

Mineral separates were purified by a combination of heavy liquids and magnetic methods followed by hand picking under a binocular microscope; purity
was checked optically and by X-ray diffraction; all oxygen and all deuterium, except for the Porphyry Mountain sample, were analyzed at the Geological
Survey of Japan using analytical methods described in Hedenquist et al. (1998); deuterium of the Porphyry Mountain sample was analyzed at Oregon State
University using methods described by Bigeleisen et al. (1952); temperatures for Big Gossan pyroxene and amphibole are based on pressure-corrected fluid
inclusion measurements (Meinert et al., 1997); temperatures of skarn minerals at Mines Gaspé are based on limited fluid inclusion and phase equilibria
data from Allcock (1982) and Shelton (1983); calculated fluid compositions for amphibole are based on fractionation factors of Bottinga and Javoy (1975)
and Suzuoki and Epstein (1976), and for garnet and pyroxene, the fractionation factors of Zheng (1993); the water content of amphibole was determined
by manometric measurement of H2 after reduction of the structural H2O released during stepwise heating to >1,000°C, reproducible to 0.1 wt % H2O;
this does notinclude absorbed water, which was removed by outgassing under vacuum pumping for 1–2 h at ~150°C; Flinc = fluid inclusion, # = calcite
inclusions, * = HCl leached

skarn ore deposits form as the result of wall-rock interaction
with huge amounts of hydrothermal fluid. Such fluid has an
origin not only from the immediate dike or stock intrusion but
also comes from a parent magma chamber at a depth below
the ore deposit. This generalization of a magmatic fluid
source is accepted, at least during the prograde stage (Ein-
audi et al., 1981). As a result of the fluid domination of the
system, the original host rock in the immediate vicinity of the
intrusive focus of hydrothermal fluid flow will soon have little
effect on the isotopic mass balance of the skarn minerals.
Thus, these skarn minerals should indicate the composition of
the hydrothermal fluid, at least those in a proximal position to
the intrusion.
The fluid associated with prograde skarn formation at both
Big Gossan and Mines Gaspé was a high- temperature
(350°–500°C), hypersaline liquid (up to 50–60 wt % NaCl +
KCl). The calculated δ18O value of the fluid in equilibrium
with garnet and pyroxene from both deposits is within the

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 FORMATION OF Cu-Au SKARN BY MAGMATIC FLUIDS
range of values for magmatic fluids (Taylor and Sheppard,
1986), and even minerals with minor calcite inclusions devi-
ate only slightly toward marine carbonate values of 21 to 25
per mil (Fig. 6). The δD values of amphibole are also typical
of the range for igneous minerals (Taylor and Sheppard,
1986), although they deviate to relatively light compositions.
The fluid associated with the retrograde alteration stage is
lower temperature (~350°–400°C) and lower salinity (avg 7
wt % NaCl equiv) than that of the prograde skarn fluid. Cal-
culated δ18O and δD fluid compositions from Big Gossan am-
phibole (Table 1) are in the range typical of magmatic fluid
dissolved in a felsic melt (Taylor, 1986), with no clear trend
toward measured values for local meteoric water (Fig. 7). The
amphibole samples from Mines Gaspé record a wider range
of δD fluid compositions, from –24 to –89 per mil. This wide
range may record the degassing of the parent magma cham-
ber, as this process results in fractionation such that the resid-
ual water in the melt has lighter δD values (Suzuki and Ep-
stein, 1976). As a result, the δD values of fluid exsolved at a
later stage will be progressively lower in δD whereas the δ18O
values remain relatively constant (Taylor, 1986, 1988; Bow-
man, 1998; Hedenquist et al., 1998).
Interaction of the fluid with wall rock cannot account for
this large variation in δD values where the δ18O values remain
constant, except possibly at unreasonably low water-to-rock
ratios that may characterize only the very earliest stage of
-5 0 5 10 15 20
Big Gossan
Garnet
Pyroxene
Marine Carbonate
Amphibole
Amphibole
with calcite
Gaspé inclusions
Garnet
Pyroxene
Amphibole
Igneous
amphibole
Magmatic
fluid
-5 0 5 10 15 20
δ18 O (0/ 00, VSMOW)
FIG. 6. Calculated δ18O (VSMOW) composition of fluids in equilibrium
with garnet, pyroxene, and amphibole from the Big Gossan and Mines Gaspé
skarn deposits. See Table 1 for data and sources of fractionation factors. The
average composition of magmatic fluid and the marine carbonate values are
from Taylor (1986) and references therein.
0361-0128/98/000/000-00 $6.00
153
alteration, i.e., ratios <0.01 (Bowman, 1998). A small, <10
percent, meteoric water component could account for slight
variations in the range of δ18O composition, <2.5 per mil at
each deposit; however, such a small diluent could not be re-
sponsible for the greater than six-fold decrease in salinity
from the prograde hypersaline fluid to 7 wt percent NaCl
fluid during the retrograde stage.
In some cases a large variation in salinity of the exsolved
fluid can occur according to the degree of crystallization, but
this is critically dependent on the pressure (Cline, 1995). We
argue that the porphyry situation modeled by Shinohara and
Hedenquist (1997), in which there is a relatively small varia-
tion in the salinity of the bulk fluid, may apply here during
much of the crystallization and exsolution. By contrast, the
trend in the δD composition of residual water during crystal-
lization will always be toward lower values (Suzuki and
Epstein, 1976). Indeed, the residual water fixed by primary
hydrous minerals, with intrusions typically having concentra-
tions of 0.5 to 1 wt percent water, are observed to have δD
values <–100 per mil as the result of late open-system de-
gassing (Taylor, 1986, 1988; Hedenquist and Richards, 1998).
This observation suggests that the formation of retrograde
alteration minerals in general, and amphibole- epidote in par-
ticular, can result from evolution of a single magmatic hy-
drothermal system, since there is no evidence in the Big Gos-
san skarn system for mixing with a significant component of
meteoric water. The sharp decrease in salinity, from prograde
hypersaline brine to a retrograde salinity of about 7 wt per-
25 cent NaCl, can be explained if the later fluid followed a cool-
ing path where it never intersected its solvus (Fig. 8). In this
situation, a hypersaline liquid would not form, and the salin-
ity of the fluid that reaches the ore deposit is that of the bulk
salinity of the exsolved magmatic fluid (Meinert et al., 1997;
Shinohara and Hedenquist, 1997; Hedenquist et al., 1998).
Such a scenario would result in a zonation in both space and
time not only of the skarn mineralogy, as described earlier,
but more fundamentally of the fluid from which those miner-
als precipitated (Fig. 8).
Model of Evolution
Upon initial intrusion of the parent magma to shallow
depths the temperature of both magma and immediately
adjacent wall rocks was >400°C, the normal limit of brittle
behavior. Thus, the rocks behaved in a ductile fashion, sealing
the system from significant interaction with connate and me-
teoric waters (Fournier, 1992). As the pluton cooled and crys-
tallized at depths of, say, 4 to 5 km (Fig. 8), the melt eventu-
ally saturated with respect to an aqueous fluid, which was a
supercritical fluid with a moderate salinity of 6 to 8 wt percent
(Burnham, 1979; Yang and Bodnar, 1994; Bodnar, 1995). This
fluid ponded near the crystalline shell of the magma chamber
at a subsolidus temperature of about 600°C (Burnham and
25 Ohmoto, 1980; Fournier, 1987). Subsequent fluid ascent to
shallower depths probably was concurrent with intrusion of
porphyry dikes to approximately 2 to 3 km beneath the paleo-
surface, with the dikes providing the permeability to focus the
advective ascent of exsolved magmatic fluid.
The combination of high fluid flux and thermal mass of the
dikes kept the early fluid relatively hot during ascent, with
only minor conductive cooling (Shinohara and Hedenquist,
153
154 MEINERT ET AL.

25
Initial water
0 Big Gossan skarn dissolved in melt
amphibole
δD (0/ 00, VSMOW) -25 Gaspe skarn
amphibole
-50 Gaspe igneous

Degassing
amphibole
-75

-100

-125
Present-day
-150 Ertsberg meteoric
water, snow, & ice
-175
-25 -20 -15 -10 -5 0 5 10 15
δ18 O (0/ 00, VSMOW)
FIG. 7. Calculated δ18O versus δD compositions of fluids in equilibrium with amphibole (Table 1) from the Big Gossan
and Mines Gaspé skarn deposits. The field for water initially dissolved in silicate melt is from Taylor (1992). As water exsolves
from magma, the δD of residual water remaining in the melt becomes lighter (Suzuoki and Epstein, 1976). Therefore, the
δD of late exsolved water is lower (Taylor, 1986; Hedenquist and Richards, 1998). Values for present-day meteoric waters
from the Ertsberg district are from Harrison et al. (1999).

200 400
T°C 600 800

Na:K = 1:1
1 Vapor
Liquid +
Liquid
20 2 Vapor + Salt
1 1
0.
Depth (hydrostatic)

40 4 0.2
7
Pressure (MPa)

5 Skarn 2
80

0.5
wt

Retrograde 10
%

60 6 alteration with
qtz-anhydrite,
amphibole, 1.0
FIG. 8. Composition of coexisting liquid and vapor as a function
and sulfides
Depth (lithostatic)

of depth and temperature (after Fournier, 1987). Isopleths of

60

3 NaCl in liquid (dark lines) and vapor (light lines) are shown for
wt%

80 compositions of interest. Two different cooling paths are shown for

an initial liquid composition of 7 wt percent NaCl. The liquid that
ascends along the “skarn” trajectory hits its solvus at about 500°C
20 and a pressure of 50 MPa (lithostatic pressure at a depth of about
40 w

2 km). Continued depressurization results in the separation of a

NaCl in liquid small amount of hypersaline liquid with a low-salinity vapor domi-
t%

100 4 nating the mass of the two-phase fluid. The later liquid that as-
cends along the “retrograde” trajectory intersects its saturated
vapor-pressure curve at about 370°C and a hydrostatic pressure of
6-8 wt% 20 MPa, also equivalent to a depth of about 2 km. At this point the
NaCl fluid begins to boil, with a small amount of vapor separating to
leave the residual liquid slightly higher in salinity.

0361-0128/98/000/000-00 $6.00 154

 FORMATION OF Cu-Au SKARN BY MAGMATIC FLUIDS
1997). The highest temperature and lithostatic pressure de-
duced for the formation of these deposits during their pro-
grade stage is 535°C and 50 MPa, respectively (Meinert et al.,
1997). This is consistent with the steep isotherms around a
near-solidus magma that is exsolving an aqueous fluid (Shino-
hara and Hedenquist, 1997). A magmatic fluid with bulk
salinity of 7 wt percent NaCl will intersect its solvus at a 2-km
depth and separate into a 50 wt percent hypersaline liquid in
equilibrium with a vapor containing ~1 wt percent NaCl (Fig.
8). Based on the fluid inclusion evidence for temperature and
salinity, most prograde skarn formed from this hypersaline
liquid.
Upon aqueous phase separation, most of the SO2 and HCl
from the parent fluid will partition into the vapor phase (Can-
dela and Piccoli, 1995; Scaillet et al., 1998; Keppler, 1999),
which being less dense forms a vapor plume overlying the
reservoir of hypersaline liquid that is generated (Henley and
McNabb, 1978). This creation of a hypersaline liquid with
high base metal solubilities and relatively low sulfur content
may have inhibited sulfide deposition during formation of the
prograde skarn, similar to Bodnar’s (1995) argument for por-
phyry deposits. Condensation of much of the vapor plume at
shallow depths would have formed a highly acidic, low-salin-
ity liquid which most likely would have caused advanced
argillic alteration (Hedenquist, 1995) and dissolution of the
host carbonate rocks with attendant brecciation, again analo-
gous to formation of volcanic-hosted lithocaps over porphyry
deposits (Hedenquist et al., 1998). This can be thought of as
the ground-preparation stage of a growing skarn system in
which the vapor plume produces cavernous porosity in car-
bonate rock, to be overrun subsequently by the high- salinity,
skarn-forming fluid as the system expands. Thus, the many
breccias that occur at both Big Gossan and Mines Gaspé, as
well as at other skarn deposits in the porphyry environment
(Einaudi, 1982), are part of the normal early-stage hydrother-
mal evolution of such systems.
As the underlying vapor-saturated magma chamber contin-
ued to cool and crystallize, fluid continually exsolved, and this
later fluid may have been relatively similar in bulk Na-K-Cl
composition to that of the earlier stage fluid (Cline, 1995; Shi-
nohara and Hedenquist, 1997). However, because of the lack
of concurrent dike intrusion and/or a sharply lower fluid flux
as the parent magma approached the end stages of stagnant
crystallization (Shinohara and Hedenquist, 1997), the ascend-
ing fluid followed a cooling path different from that of the
early stage. The lower rate of advection (Shinohara and
Hedenquist, 1997) meant that this late fluid cooled suffi-
ciently during ascent so that it never intersected its solvus
(Fig. 8).
Cooling to a temperature below approximately 400°C results
in a transition from ductile to brittle rock behavior, causing a
change from lithostatic to hydrostatic conditions (Fournier,
1991). Thus, even though the later stage fluid reached the
previously formed skarn at the same paleodepth of 2 km, the
pressure was 20 MPa under the hydrostatic conditions. A 7 wt
percent NaCl liquid at 20 MPa will intersect the saturated
vapor-pressure curve at 370°C, resulting in boiling of the as-
cending liquid. Continued boiling and vapor loss will result in
progressive cooling accompanied by only a slight increase in
salinity due to vapor loss, e.g., from 7 to 10 wt percent NaCl
0361-0128/98/000/000-00 $6.00 155
155
on boiling from 370° to 320°C (Henley et al., 1984). At this
shallow depth and relatively low temperature, dissolved gases
will be lost to the vapor, possibly explaining sulfide mineral-
ization from the low-salinity fluid that occurs during this late
stage.
This general scenario (Fig. 8) illustrates only two snap-
shots of a dynamic system. In reality, multiple intrusions—
into the parent chamber and as shallow dikes—combined
with fluctuations in the water table due to structural, paleo-
surface, and/or climatic changes (e.g., Simmons, 1991)
would have caused a more complex overprinting of various
skarn and retrograde alteration stages. These changes are
seen in the rock record as a series of crosscutting features
and zonation patterns that are typical of skarn and intrusion-
centered ore deposits worldwide (Einaudi et al., 1981; Ben-
dezú and Fontboté, 2002; Rusk and Reed, 2002). Neverthe-
less, despite this complexity we conclude that the fluid
responsible for prograde and retrograde alteration as well as
ore formation was dominantly magmatic in origin. Similar
conclusions have been reached for porphyry copper de-
posits which formed largely within igneous rocks (e.g.,
Kusakabe et al., 1990; Shinohara and Hedenquist, 1997;
Hedenquist et al., 1998; Watanabe and Hedenquist, 2001;
Harris and Golding, 2002). Here we extend such conclu-
sions to skarn deposits in which hydrothermal fluids have es-
caped the igneous carapace and interacted extensively with
surrounding wall rocks.
Acknowledgments
This work was partially supported by National Science
Foundation grant EAR-9725437. The senior author’s visit to
the Geological Survey of Japan was facilitated by a Japan So-
ciety for Promotion of Science short-term invitation fellow-
ship, administered by the National Science Foundation. We
thank Steve Rowins, John Bowman, and John Dilles for help-
ful comments on earlier versions of this paper.
April 5, October 17, 2002
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