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CHRISTOPH A. HEINRICH
ETH Zrich, Isotope Geochemistry and Mineral Resources, Department of Earth Sciences, ETH Zentrum NO, 8092 Zrich, Switzerland,
and Faculty of Mathematics and Natural Sciences, University of Zrich, Ramistrasse 17, 8006 Zrich, Switzerland
Abstract
The chemical and physical evolution of magmatic to hydrothermal processes in the porphyry Cu-Au deposit
of Bajo de la Alumbrera (northwestern Argentina) has been reconstructed with a quantitative fluid inclusion
study. Fluid inclusion petrography, microthermometry, and single inclusion microanalysis by Excimer laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are combined to determine the evolution
of pressure, temperature, and ore metal concentrations (including Cu and Au) in the fluids. Complementary
hydrogen and oxygen isotope analyses are used to further constrain the water sources in the evolving system.
The combined data provide a new level of insight into the mechanisms of metal sourcing and ore mineral precipitation in a porphyry-style magmatic-hydrothermal system.
Based on previously reported observations of the igneous geology, alteration geochemistry, and veining history of the subvolcanic porphyries at Alumbrera, the distribution of fluid inclusion types in space and time is
documented. Six major inclusion types are distinguished. The highest temperature brine inclusions (up to
750C; P >1 kbar) are mainly recorded in barren quartz magnetite veins in the core of the alteration system.
These polyphase brine inclusions (halite sylvite + multiple opaque and transparent daughter crystals) are interpreted as the most primitive magmatic fluid recorded at the level of the deposit. They are of moderately
high salinity (5060 wt % NaCl equiv) dominated by NaCl, KCl, and FeCl2, and contain on average 0.33 wt
percent Cu and 0.55 ppm Au. Upon cooling and decompression, these saline liquids exsolve a vapor phase,
which is preferentially enriched in Cu relative to its main salt components but probably plays a minor role in
the formation of this particular deposit because of the inferred small mass fraction of vapor. Cooling and decompression from the highest initial P-T conditions down to about 450C causes magnetite K silicate alteration but no saturation in Au or Cu sulfides, as recorded by continually high ore metal concentrations in the
fluid inclusions. Coprecipitation of Cu and Au as chalcopyrite and native gold ( some early bornite) occurs
over a narrow range of decreasing fluid temperature. With cooling from ~400 to 305C, the Cu concentration
in the brine drops by about one order of magnitude to less than ~0.07 wt percent, without a proportional decrease in major salt components. Ore mineral precipitation extracts ~85 percent of the Cu and Au from the
fluid. It is associated with potassic alteration, as shown by a concomitant decrease in the K/Na ratio of the cooling magmatic brine and by an increase in its Ba and Sr concentrations (elements which are probably liberated
in the destruction of calcic igneous minerals).
The fluid chemical data demonstrate that the metal ratios in this and probably many other porphyry-style
ore deposits are primarily controlled by the magmatic source of the ore brines. On the other hand, the final hypogene ore grade of the deposit is controlled by the efficiency of ore mineral precipitation. At Alumbrera,
metal extraction is governed by the efficiency of cooling a high flux of magmatic fluid within a small rock volume. Dilution of residual magmatic fluids, as recorded by aqueous fluid inclusions of decreasing salinities and
temperatures below 295C, follows after the main stage of copper introduction and is associated with feldspardestructive (phyllic) alteration. Geometric relationships, fluid analyses, and stable isotope data together indicate that phyllic alteration results from postmineralization hydrothermal activity involving minor mixing between meteoric water, residual brine, and a waning input of magmatic vapor.
Introduction
HYDROTHERMAL fluid transport associated with shallow
crustal magmatism is a key process contributing to the formation of major metal resources. Among the magmatic-hydrothermal ore deposits, porphyry Cu-Au-Mo deposits are
the economically most important today and have been the
Corresponding
1743
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ULRICH ET AL.
ences therein) and more recent microanalytical data (Diamond et al., 1990; Boiron et al., 1991; Heinrich et al., 1992;
Mavrogenes et al., 1995; Damman et al., 1996) show that
magmatic fluid inclusions can contain very high ore metal
concentrations. With the recent development of laser ablation-inductively coupled plasma-mass spectrometry (LAICP-MS; Gnther et al., 1998; Audtat et al., 2000a, b), a single inclusion analytical technique of sufficient sensitivity,
quantitative accuracy, and routine applicability has become
available for extensive studies of texturally complex samples
(Audtat et al., 1998). In this paper we report the first study
of a world-class magmatic-hydrothermal ore deposit, where
LA-ICP-MS analyses of some 300 individual fluid inclusions
in 27 samples are integrated with conventional fluid inclusion
techniques and other geochemical data within a good geologic framework, as reported in Ulrich and Heinrich (2001).
The aim of this study is to quantify the behavior of ore metals
and other elements involved in hydrothermal mass transfer
by high-temperature brines, vaporlike fluids, and low-salinity
aqueous solutions. By combination with stable isotope data
we determine the sources of fluids and metals independently
and define the mass transfer and the dominant causes for
metal precipitation in the orebody.
Geologic Setting
The Cu-Au deposit of Bajo de la Alumbrera in northwestern Argentina (lat 2730' S, long 6660' W) is hosted by several high K dacite porphyries that intruded into andesitic
flows and pyroclastic rocks of the Faralln Negro Volcanic
Complex. From crosscutting relationships and petrographic
observations, several porphyries can be distinguished (Table
1) that form a composite intrusive complex (Ulrich and Heinrich, 2001; J. M. Proffett, writ. commun.). The Ar/Ar dates of
biotite from the earliest mineralized P2 Porphyry (7.10
TABLE 1. Relative Timing Relationships between the Porphyry Intrusions at Bajo de la Alumbrera
Porphyry
Timing relationships
Alteration/mineralization
NE Porphyry
P2 Porphyry
Early P3 Porphyry
Quartz-Eye Porphyry
Late P3 Porphyries
(Campamiento and
North Porphyries)
Post-Mineral Porphyry
Summary of the geologic relationships among the different porphyry intrusions; for a complete description of the geology see Ulrich and Heinrich (2001)
and J.M. Proffett (unpub. data)
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0.13) and a postore dike (6.83 0.07 Ma) constrain the late
Miocene age of mineralization (Sasso and Clark, 1998). The
P2 and the Early P3 Porphyries are the two distinct intrusions
hosting the bulk of the economic copper-gold mineralization,
which was introduced by at least two separate magmatic-hydrothermal fluid pulses into a dense network of quartz magnetite-chalcopyrite veinlets. The slightly later Quartz-Eye
Porphyry is overprinted by a stockwork of characteristic pink
quartz veins that are associated with intense feldspar-destructive alteration in outcrops. These veins contain only minor
bornite and chalcopyrite. At least four subsequent stages of
minor intrusion are weakly altered and essentially unmineralized, and all have much lower vein densities than the P2, the
Early P3, and the Quartz Eye Porphyries (Ulrich and Heinrich, 2001; J. M. Proffett, writ. commun.; Table 1).
The alteration sequence is characterized by an early quartzmagnetite assemblage in the center of the deposit. This alteration is concentrated on the P2 Porphyry, but a second
weaker phase of this alteration also affects parts of the Early
P3 Porphyry. The adjacent potassic alteration (K feldspar +
biotite magnetite) is most intensely developed in the mineralized porphyries but affects in a less intense form (secondary biotite) some of the later intrusions, such as the
Northwest Porphyry dikes. This alteration is surrounded by a
propylitic zone at the fringe of the deposit, overprinting
mainly the andesitic volcanic rocks and some porphyry dikes.
Concentric zones of quartz-magnetite, potassic, and propylitic alteration of the mineralized stock and all later intrusions
are overprinted by feldspar-destructive alteration, which advanced from the top of the deposit downward along steep
crosscutting structures and lobes. Mineralization is dominated by chalcopyrite and intimately intergrown gold. Ore
mineral precipitation is associated with potassic alteration and
occurs as disseminations in the porphyries and proximal andesitic volcanic rocks and as texturally late phases in quartz
magnetite veinlets. Economic Cu and Au concentrations
occur in a high-grade ore shell above and around a barren
core of highly quartz-magnetite-altered but sulfide-poor
porphyries.
Sample Material for Fluid Inclusion and Isotope Studies
Samples with veins and phenocrysts for petrographic, fluid
inclusion, and stable isotope studies were taken from original
surface outcrops and the developing mine, but most samples
were collected from diamond drill core (Appendices 1 and 2).
The selection of samples was based on core logging and surface mapping of the main alteration zones (quartz-magnetite,
potassic, propylitic, and feldspar-destructive alteration) and
the distribution of high Cu-Au grades. The vertical sampling
extends to a depth of 550 m below the premining land
surface.
Vein densities and crosscutting relationships were most
clearly observed in the P2, Early P3, and the Quartz-Eye Porphyries. Fluid inclusion and isotope data were derived from
samples of the major vein and alteration types in these intrusions. The Early P3 Porphyry is intimately associated with the
second major pulse of mineralization and potassic and quartzmagnetite alteration. It provided the preferred and some of
the best fluid inclusion material. Exceptionally well preserved
fluid inclusions were also found in a 5- to 8-cm-thick vuggy
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vein of coarse-grained purple quartz from a block of QuartzEye Porphyry in the southeastern part of the open pit (sample BLA97). Euhedral crystals up to 1 cm contain inclusion
assemblages in a particularly clear time sequence. Biotite inclusions indicate that this quartz crystallized during potassic
alteration. Pyrite and possibly anhydrite (now gypsum) were
deposited later in the vugs, associated with feldspar-destructive overprint of the wall rock.
Fluid inclusion assemblages in the small quartz veinlets related to feldspar-destructive and chlorite-epidote alteration
were inadequate for analysis. Suitable inclusions probably representing the feldspar-destructive stage were observed on secondary trails in strongly feldspar destructively overprinted
samples, even though the quartz host in these samples belongs
to veins of the potassic stage. Secondary trails are very common in these samples and cut trails of primary or pseudosecondary inclusions preserved from the potassic veining stage.
For a reconnaissance stable isotope study, selected minerals were separated from veins and whole-rock samples to obtain an enriched mineral fraction of 90 percent purity or
more. Fluid inclusion samples were also used for isotopic
analysis, as far as possible. Quartz phenocryst separates of the
least altered intrusion of the Northwest Porphyry were analyzed to obtain an isotopic signature representative for the
magmas. Coexisting quartz and magnetite from the quartzmagnetite alteration zone were used to estimate both the
18O composition and the temperature conditions of the earliest alteration stage at Alumbrera. To estimate the oxygen
isotope composition of fluids associated with the main alteration zones, we analyzed the quartz veins related to potassic
alteration in three samples of the Early P3 and Quartz-Eye
Porphyries and quartz separates from late veinlets and matrix
quartz associated with feldspar-destructive alteration. Secondary biotite was analyzed for 18O in three wall-rock andesites with intense potassic alteration, and two albite samples were analyzed to represent the chlorite-epidote zone.
Hydrogen isotopes were determined on biotite of potassically altered rocks, on chlorite of the chlorite-epidote zone,
and sericite and/or clay fractions from samples with feldspardestructive overprint. Hydrogen isotopes of fluid inclusions
were analyzed after thermal extraction of inclusion water
from veins related to the quartz-magnetite, the potassic, and
the feldspar-destructive alteration.
To obtain an estimate of the local meteoric water at the
time of hydrothermal activity, we analyzed quartz and fluid
inclusion extracts from the post-sulfide stage of an epithermal
vein of the Faralln Negro gold mine, located 15 km northwest from Alumbrera along the same structural trend
(Malvicini and Llambias, 1963).
Petrography and Distribution of Fluid Inclusions
Fluid inclusion types
Petrography and all subsequent single inclusion measurements strictly concentrated on fluid inclusion assemblages,
i.e., closely associated groups or trails of inclusions with visually identical phase ratios and similar shape (Goldstein and
Reynolds, 1994). Six types of fluid inclusions were distinguished according to the number, the nature, and the volume
proportions of phases present at room temperature (Fig. 1).
1745
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ULRICH ET AL.
polyphase brine
opaque-bearing brine
brine
halite
hematite
halite
halite
20m
20m
A
aqueous
20m
B
high-density
20m
20m
lowdensity
chalcopyrite
20m
Vein quartz
Low-density
vapor inclusions
High-density
vapor inclusions
Quartz phenocryst
50m
20m
Polyphase
brine inclusions
Low-density
vapor inclusions
Low-density
vapor inclusions
Polyphase
brine inclusions
20m
50m
FIG. 1. Photomicrographs of inclusion types and relative timing among assemblages. A. Polyphase brine inclusion with
hematite and three unidentified daughter phases. B. Opaque-bearing brine inclusion characterized by one or two opaque
daughter crystals. C. Simple brine inclusions containing only a halite daughter crystal, which has a similar or slightly larger
size than the vapor bubble. D. Two-phase aqueous inclusion (325 m) with a larger or similar proportion of liquid than
vapor. E. High-density vapor inclusions, commonly with a chalcopyrite crystal (1545 m). F. Low-density vapor inclusions
containing more than 80 percent vapor. G. A low-density vapor trail is cut by a similar trail with small high-density inclusions
(sample BLA97). H. Fluid inclusion relationship in a phenocryst that is crosscut by a quartz veinlet (stippled line shows the
contact). The small polyphase and opaque-bearing brine inclusions (I) occur exclusively in the phenocryst (see also Fig. 2A).
J. and K. Trails of small polyphase brine inclusions are cut by later low-density vapor trails.
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ULRICH ET AL.
Sample 45-61.3 S
magnetite
pyrite
phenocryst
high-density
vapor inclusions
vein quartz
high-density
vapor inclusions
high-density
vapor inclusions
polyphase and
high-density
vapor inclusions
aqueous
inclusions
polyphase brine
inclusions and
low-density
vapor inclusions
polyphase
brine inclusions
heterogeneous
trapping of vapor-rich
and polyphase
brine inclusions
secondary polyphase
brine inclusions
low-density
vapor inclusions and
polyphase brine inclusions
1 mm
low-and high-density
vapor inclusions
high-density
high-density
vapor inclusions vapor inclusions and opaquebearing brine inclusions
biotite
low-density
vapor inclusions
small polyphase and
opaque-bearing brine
inclusions,some
high-density
vapor inclusions
opaque-bearing
brine inclusions
1 mm
FIG. 2. A. Sketch of a phenocryst cut by a veinlet (sample 45-61.3 S). Small, hematite-bearing inclusions (smallest dots)
are restricted to the phenocryst, whereas later generations of polyphase and opaque-bearing brine inclusions also occur in
the vein. B. Simplified drawing of crystals from sample BLA97 showing the relative timing relationships of saline and vapor
inclusions. The polyphase and opaque-bearing brine inclusions occur in the core, whereas the vapor inclusions are on trails
and commonly along the outer zone of the crystal.
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51-61.1/6
51-61.1/11
47-55.3/10
51-61.1/5
45-61.3/13
47-55.3/7
47-55.3/9
51-52.2 /9
51-52.2 /11
51-52.2/13
51-52.2/14
47-53/48
49-50.1/4
49-50.1/8
51-61.1/8
50.3-59.4/8
47-53/72
49-52/3
49-52/19
47-53/25
47-53/30
47-53/62
49-52/10
49-52/21
49-50.1/1
49-61.4/16
49-61.4/19
50.3-59.4/6
49.2-46.3/4
49.2-46.3/5
49.2-46.3/8
49-52/9
49-52/14
49-51/1
49-51/3
49-51/5
BLA 97
BLA 18
AK
AM
J
AJ
A
H
I
AF
AG
AH
AI
D
M
N
AL
AE
F
R
V
B
C
E
T
W
L
Y
Z
AD
AA
AB
AC
S
U
O
P
Q
AO
AN
Surface
Surface
146
413
226
334
118
128
311
260
337
354
277
283
89
278
279
292
242
315
182
184
192
524
547
147
523
428
110
146
204
211
212
224
226
357
371
537
Depth
(m below
surface)
0.74
0.51
0.05
0.10
0.06
0.10
0.30
0.08
0.05
0.05
0.58
1.40
0.72
0.80
0.80
0.77
0.06
0.14
0.94
0.85
0.91
0.02
0.01
1.40
0.02
1.40
0.50
1.40
0.01
0.04
0.04
0.11
0.56
0.09
0.05
0.01
1.28
0.75
0.14
0.06
0.10
0.17
0.23
0.06
0.05
0.02
0.80
1.94
2.12
0.53
0.53
0.71
0.05
0.16
1.55
1.50
1.48
0.03
0.02
1.95
0.03
2.43
0.78
1.95
0.02
0.09
0.09
0.11
0.40
0.04
0.05
0.07
Ore grades
Cu
Au
(wt %) (ppm)
Quartz-magnetite, Early P3
Quartz-magnetite, Early P3
Quartz-magnetite, Early P3
Potassic with quartz-magnetite, Early P3
Potassic, Early P3
Potassic, Early P3
Potassic, Early P3
Potassic, Early P3
Potassic, Early P3
Potassic, Early P3
Feldspar destructively overprinted, Early P3
Feldspar destructively overprinted, Early P3
Feldspar destructively overprinted, Early P3
Feldspar destructively overprinted, Early P3
Feldspar destructively overprinted, Early P3
Feldspar destructively overprinted, Early P3
Slightly feldspar destructively overprinted, Early P3
Slightly feldspar destructively overprinted, Early P3
Slightly feldspar destructively overprinted, Early P3
Slightly feldspar destructively overprinted, Early P3
Slightly feldspar destructively overprinted, Early P3
Quartz-magnetite, P2 Porphyry
Quartz-magnetite, P2 Porphyry
Quartz-magnetite, P2 Porphyry
Quartz-magnetite with calcite filling, P2 Porphyry
Potassic with quartz-magnetite, P2 Porphyry
Potassic, P2 Porphyry
Potassic, P2 Porphyry
Potassic, P2 Porphyry
Potassic, P2 Porphyry
Potassic, P2 Porphyry
Potassic, P2 Porphyry
Potassic, P2 Porphyry
Potassic, P2 Porphyry
Potassic, P2 Porphyry
Potassic, P2 Porphyry
B
B
10
50
5
10
15
5
40
55
10
10
15
15
30
5
10
20
20
15
30
5
60
10
35
10
10
40
25
35
50
25
60
50
50
45
10
55
40
25
Polyphase
(%)
15
15
5
25
10
5
20
30
30
10
20
5
40
50
10
25
5
15
25
15
10
5
5
25
5
25
10
Opaque
bearing
(%)
5
5
10
5
50
10
5
5
15
5
5
10
15
15
10
60
25
20
10
45
15
15
20
30
10
5
35
60
Aqueous
(%)
30
5
45
35
15
15
10
5
5
15
20
10
5
25
Brine
(%)
50
20
5
5
15
5
5
5
10
10
25
25
20
20
10
5
10
30
20
25
10
10
5
15
20
10
10
40
15
10
5
5
10
25
10
60
50
20
10
10
15
5
15
25
15
55
60
50
25
60
55
20
15
30
40
40
20
5
40
30
10
35
50
25
10
15
10
25
15
30
20
Vapor inclusions
HighLowdensity
density
(%)
(%)
Selected samples that were used to delineate the distribution of the different inclusion types in the deposit; the abundance of each inclusion type was estimated optically from double-polished sections; sample ID refers to the frequency diagrams of Figure 3; B = sample with boiling assemblage
Drill hole
Sample
ID
(Fig. 3)
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ULRICH ET AL.
TABLE 3. Nomenclature of Fluid Inclusion Measurements
Th(L)
Tm(halite) > Th
Th(V)
Tm(ice)
Tm(CO2)
Tm(halite)
assumed for the analyzed inclusions. Measuring several assemblages of identical petrographic appearance within one
section generally showed consistent homogenization temperatures, indicating that this assumption is valid.
Results
The highest temperature was measured in an assemblage of
opaque-bearing brine inclusions that homogenize to the liquid at 771 16C (assemblage 92, Table 4). In general, highest homogenization temperatures of polyphase brine and
Sample
49-52 19A
46-59QZE
49-52 14
51-61.1 II,5/1
49-52 3/3
49-52, 19B/3
49-52, 19b/3 IV
45-61.3, 13/1
49-50,1, 1/8
49-52 3/3
49-50,1, 4/6
47-53, 62/1
49-52,21/3
49-51, 5/5
BLA1/97A I,2
51-61.1, 5/ 3
51-61.1, 5 IV
47-53/25B
51-61.1 5 I
BLA1/97B,2
47-53 25B
BLA1/97B I,1
51-52,2, 13
BLA1/97B,2
BLA1/97A,1
BLA1/97A,1
BLA1/97B2
BLA IV 97, 3/1
Avg BLA IV 97, 3
BLA IV 97, 2/6
BLA2/97 B2
BLA 1/97B II,1
BLA2/97B2
Salinity (wt %
NaCl equiv)
3 0.3
7.1 4.2
1.4 0.3
17.7 0.1
35 0.5
41.4 3.9
42.1 3.7
43.9 2.8
41 4.7
48.4 4.0
46 3.8
44 0.3
48.4 6.0
50.9 4.3
52.7 3.0
49.9 1.8
50 0.6
61.7 2.5
45.1 3.3
71.1 0.2
61.4 2.9
36.9 2.8
52 0.4
65.5 2.1
63.8 1.9
58 1.1
66.1 3.6
64 1.6
62 1.2
56 4.0
53 1.5
36.9 2.8
46.5 3.0
240 0.3
242 2.6
271 20.7
292 10.0
305 5.0
368 39.6
387 43.2
397 6.5
400 14.1
419 26.2
421 1.0
423 22.5
448 3.5
463 19.0
470 14.1
471 18.4
499 12.6
530 0.3
540 69.1
580 3.0
6652
671 6.0
7203
7203
7202
7202
7222
7223
7223
7223
7302
7303
771 16.3
P (bars)
Basis for P
estimate
50
50
80
80
80
2810/1501
150
180
200
250
220
220
270
320
320
340
380
370
530
1135/3801
620
1100
1050
680
750
900
680
750
800
950
1080
1280
1320
LV curve
LV curve
LV curve
LV curve
Boiling curve
Halite disappearance
LV curve
Boiling curve
Boiling curve
Boiling curve
Boiling curve
LV curve
Boiling curve
LV curve
Boiling curve
LV curve
LV curve
Boiling curve
LV curve
Halite disappearance
LV curve
LV curve
Boiling curve
Boiling curve
Boiling curve
Boiling curve
LV curve
LV curve
LV curve
LV curve
LV curve
LV curve
LV curve
Microthermometric data and pressure estimate of boiling assemblages and single-phase assemblages that are shown in Figure 6 and which were subsequently analyzed by LA-ICP-MS; sorting of the table is based on increasing homogenization temperatures (roughly corresponding to a sequences of late to
early assemblages); pressures for nonboiling assemblages are minimum pressures
1 Pressure calculated according to Bodnar (1994) for halite homogenizing inclusions and the assumed pressure, respectively (see text for explanation)
2 Single analysis due to decrepitation of inclusions from different assemblages
3 Extrapolated values from measurements of similar but different assemblages (see text for explanation)
0361-0128/98/000/000-00 $6.00
1750
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WSW
ENE
3
6.
-4
-.2
49
AO
Gypsum
Fault
50
.3
-5
9.
4
51
-6
45 1.
1
-6
49 1.4
-6
1.
4
47
-6
2
AN
1.
3
5.
-5
47
5
-5
47
3
-5
47 .2
2
-5
51 -52
49 2
-5 1
47 9-5
4
1
0.
-5
49
m a.s.l.
2600
AD
2500
AF
AH
AE
AG
AI
2400
C
S
AA
P
Y
AB
Z
W
2300
quartz-magnetite
alteration
strong K-feldsparbiotite alteration
moderate and
weak K-feldsparbiotite alteration
secondary
biotite alteration
weak secondary
biotite alteration in
late porphyries
chlorite-epidote
alteration
late feldspardestructive
alteration
Cu-grade contour
0.5 wt%
approximate
boundaries of
main porphyries
against surrounding
andesites
AC
M
ve
Ste
N
A
s
Fa
AJ
ult
2200
AK
AL
AM
average abundance
high-density
vapor incl.
polyphase
brine incl.
low-density
vapor incl.
aqueous incl.
coexisting polyphase
brine and
vapor inclusions
opaque-bearing
brine incl.
low-grade qtz-mag
alteration
core
brine incl.
potassic
80
64
70
Opaque-bearingbrine inclusions
60
Brine inclusions
Aqueous inclusions
50
High density
vapor inclusions
103
100
40
60
77
85
98
75
110 99
30
79
61
115/117
62
56
49
65-68
70
107
86
50
5155
48
81-83/87116
80
47
94 59
101 52112
96
78
95/54
106
58
74
84
109
57
90
89
88 53
97
102 76
105
108/111
69
63
72
71
114
93
113
92
91
104
5
22
5a
20
anhydrite
14
anhydrite
10
1
calcite
100
34
7
39
30
25
11/18
28/29
27
10/15/19
2624
16
36
12 40
21 4
13
6
17
8 23 20
31/32
37
38
43-46
41/42
116
33
300
200
400
Th L or by halite
melting (C)
500
600
700
800
62
0361-0128/98/000/000-00 $6.00
47
79
83
500
82
60
51
81
Tm halite (C)
900
400
99
300
100
87 74
103
98
75
110 88
200
100
100
1751
86
56
65 61/64
63
55 107
48
50
95 80 96
59
94
112 58 116/54
84
101
73
109/52
106
77 85
53 90
102 76
108/111
97
68
49
70
66/67
69
71
72
115/117
114
93
78
113
92
57
89
91
105
104
Boiling
assemblages
200
300
B
400
500
Th L (C)
600
700
800
900
1752
ULRICH ET AL.
TABLE 5. Summary of the Microthermometric Data and Estimated Pressures of the Different Inclusion Types
Description of assemblages
Microthermometry data
Pressure estimate
Deposit-scale distribution
Opaque-bearing brine
inclusions: Randomly distributed
inclusions of primary character in
phenocrystals; assemblages
homogenizing by halite
melting are later
Brine assemblages:
Only small assemblages,
trails or randomly distributed
Aqueous assemblages:
Randomly and on planes,
irregular shaped to rounded
in samples with a feldspardestructive overprint
Feldspar-destructive overprint,
peripheral areas of the deposit
Feldspar-destructive overprint,
peripheral areas of the deposit
(sylvite?) melts at 460 to 490C always before halite (e.g., assemblage 67). Such high melting temperatures are rarely reported for sylvite but were previously found in the Endeavour
26 North porphyry Cu-Au deposit at Parkes, Australia (Heithersay and Walshe, 1995), implying very high K/Na ratios up
to 1.1 by weight (Roedder, 1971; Cloke and Kesler, 1979).
In polyphase brine and opaque-bearing brine inclusions,
the opaque phases never dissolve even up to 800C. The common presence of hematite daughter crystals in hematite-free
rocks indicates H2 diffusion out of the inclusions (Mavrogenes and Bodnar, 1994). Rare, birefringent rectangular
daughter crystals (anhydrite?) also did not dissolve to at least
600C, which also may be related to postentrapment oxidation of sulfur.
Opaque-bearing brine inclusion: These assemblages are
similar in salinity and homogenization temperatures to
polyphase brine inclusions (Figs. 4A and 5B, G). Apart from
common assemblages homogenizing to liquid, there are also
assemblages in which inclusions homogenize by halite disso-
1752
0361-0128/98/000/000-00 $6.00
Polyphase
brine inclusions
Boiling
assemblage
Boiling
assemblage
Polyphase
brine inclusions
Boiling
assemblage
Polyphase
brine inclusions
115
117
62
116
47
Boiling
assemblage
114
61
Polyphase
brine inclusions
68
Polyphase
brine inclusions
Brine
inclusions
104
67
Opaque-bearing
brine inclusions
93
Polyphase
brine inclusions
Opaque-bearing
brine inclusions
91
66
Opaque-bearing
brine inclusions
Type of
inclusion
92
Assemblage
1753
Petrographic description
511.5
21.8
445.2
24.7
580.3
3.0
541.3
14.6
529.2
13.5
553.9
19.5
529.3
11.1
515.5
8.3
489.7
8.4
490.0
30.0
281.2
36.4
450.1
11.7
292.3
36.4
390.5
28.1
Tm(halite)
or Tm(ice)
665.0
470.3
14.1
488.5
3.1
>600
>600
(720)
>600
>600
>600
>600
(720)
>600
671.0
6.0
>600
>600
771.5
16.3
Th(L)
(C)
61.4
2.9
52.7
3.0
71.1
0.1
65.5
2.1
63.8
1.9
66.1
3.6
63.8
1.6
61.9
1.2
58.3
1.1
58.5
4.0
36.9
2.8
53.3
1.5
37.9
2.8
46.5
3.0
0.02
0.01
40
50
240 60
20 20
n.a.
10
10
20
202
30
20
<30 <20
n.a.
<1
4
20 n.a.
2 30
90 110 n.a.
40 30
120 10
5
20 10 1
3
1
<1
2
1
1
1
1
1
510
280
20
10
130
20
<2
<300
<25
<30
40
10
<5
5
2
<30 40
2
<10
<5
0.3
0.14
0.78
0.26
70
25
2800
120
200
50
3600
470
0.56
0.1
<1.97
60 4500
10 1300
60 4400
10
20 2000
4 110
20 1,800
2 510
20 1700
8 650
20
50 3300
5 10 100
<30
<20
60
8
3
<10
30 1600
5 270
280 <1 <10 <2 140
470
10
n.a.
7
60 n.a. 2600
3 90
480
<2
500 <10 10
<2
2
600
10
3
n.a. 50 100 20
3
10 20 20 1
<40
3
10
<1
1
1 10
170 120 20 <300 70 170
6
8
20 40 5
7 30 2 2
20 <10
2
50
1
120 n.a. 30
10
30
10 <10
2
50
b <30 12.30 7.00 1.05 10.93 0.22 0.46 <30 360 90 <110 10 <380 20
1.20 2.20 0.14 0.33 0.12 0.11
60 30
1
20
v <30 1.10 0.50 0.07 0.59 0.12 0.04 <30 30
10 <10 <2 <200 2
0.50 0.30 0.04 0.31 0.04 0.02
10 10
1
150 8.10 15.40 4.20 16.90 0.32 0.95 50 550 120 40 n.a. n.a. 40
130 1.70 2.20 0.53 2.60 0.150.17
110 20 8
10
10
20
550
50
30
10
740
50
40 12.40 11.60 1.32 15.51 0.48 0.74 <30 690 130 70 <10 340
20 1.00 0.60 0.11 1.48 0.39 0.08
80 20 20
30
0.23
0.19
0.37
0.44
10
n.a.
20
50
4 20
20 490 <1
4 170
25.20
0.50
24.30
0.60
40
n.a.
70 10.50 12.60 1.77 9.77 1.00 1.83 n.a. 960 120 220 <10
20 1.20 0.50 0.45 1.39 0.870.84
320 30 210
0.17
0.19
21.90
2.10
<50
n.a.
9.20
2.60
Salinity wt %
Li
Na
K Mn Fe Cu Zn As Rb
Sr Mo Ag Sn Cs Ba La Ce
W
Tl
Pb Au
NaCl equiv (ppm) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
1753
Boiling
assemblage
Opaque-bearing
brine inclusions
Boiling
assemblage
Brine
inclusions
112
73
106
101
0361-0128/98/000/000-00 $6.00
1754
Aqueous
inclusions
Aqueous
inclusions
Aqueous
inclusions
Aqueous
inclusions
High-density
vapor inclusion
High-density
vapor inclusion
25
21
20
32
31
Brine
inclusions
100
54
58
59
Polyphase
brine inclusions
Polyphase
brine inclusions
Polyphase
brine inclusions
Polyphase
brine inclusions
Type of
inclusion
57
Assemblage
Petrographic description
-2.0
0.4
-0.8
0.2
-2.2
0.2
-1.8
0.2
-4.6
2.9
-13.8
0.2
351.0
36.1
345.0
40.5
364.3
29.3
366.3
3.6
406.5
54.4
376.5
31.4
439.0
5.2
421.2
16.4
429.3
37.5
Tm(halite)
or Tm(ice)
430.0
8.3
270.8
20.7
399.0
23.0
240.0
242.0
2.6
292.2
10.0
219.5
27.6
386.8
43.2
397.3
6.5
423.1
22.5
447.5
3.5
540.8
69.1
499.0
12.6
471.1
18.4
462.8
19.0
Th(L)
(C)
3.4
0.7
1.4
0.3
3.6
0.4
3.0
0.3
7.1
4.2
17.6
0.1
41.4
3.9
42.1
3.7
43.9
2.8
44.0
0.3
48.3
6.0
45.1
3.3
51.9
0.6
49.9
1.8
50.9
4.3
500
300
520
110
n.a.
10
60 <10
10 70
n.a.
<3
5
5
<2
<2
3
4
490 <1
170
40
30 n.a.
30 40
<5
<10
160
30
5
10
1
n.a.
<10 <100
3
1
<0.43
200
70
<1
90
60
3 1600
1 2340
10 1,500
6 590
20
20 1800
1 5 340
<1
10 <50 <20 100
5
25
410
4
10
40
20 1200
100 6 10
6 50
90
20
<10
10
4
n.a. 1500
100
30
1
<1
1400 80
20 250 <1
610 20 2 340
<1 <100
<5
n.a.
4
2
10 2,100 3
4 3,300
<5
250
70
<5
470 70
50
20 <250 40
50 20
20
10
30 <10 <100 <70 <850 5
1
330 250 <30
6 <400 70
60 30
10
320 10.00 5.30 2.60 1.90 0.05 1.20 n.a. 500 740 <20
220 0.90 1.10 0.80 1.10 0.04 0.60
110 570
5
4
20
60 n.a.
5 10
390 50
80 n.a.
60 9 30
50 11.00 8.10 1.90 9.16 0.26 0.54 <20 490 100 130
5 <290 40
50
10
70 1.20 0.90 0.14 1.72 0.10 0.07
40
20 2
v n.a. 0.30 0.70 0.01 <0.07 0.03 0.01 <30 10
10 <30 <3 <30 <1 <15 <1
0.20 0.50
0.02
10 10
220 10.40 6.80 2.00 6.30 0.20 0.90 n.a. 400 110 60
20 n.a. 90 320 n.a.
170 0.70 0.70 0.30 1.10 0.10 0.30
100 30 15
10 40
Salinity wt %
Li
Na
K Mn Fe Cu Zn As Rb
Sr Mo Ag Sn Cs Ba La Ce
W
Tl
Pb Au
NaCl equiv (ppm) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
TABLE 6. (Cont.)
1754
ULRICH ET AL.
0361-0128/98/000/000-00 $6.00
1755
High-density
vapor inclusion
High-density
vapor inclusion
High-density
vapor inclusion
High-density
vapor inclusion
High-density
vapor inclusion
High-density
vapor inclusion
High-density
vapor inclusion
40
41
42
43
44
45
46
Petrographic description
-0.5
-0.5
-0.7
-1.0
0.1
-3.2
0.3
-3.5
1.2
-2.1
0.4
-6.3
0.8
Tm(halite)
or Tm(ice)
>600
>600
>600
>600
422.5
17.8
432.6
39.1
386.5
27.7
395.0
21.2
Th(L)
(C)
1.3
1.7
0.2
5.3
0.4
5.7
1.8
3.5
0.7
9.5
1.0
0.39
0.39
0.39
0.20
0.79
0.17
0.27
0.05
0.04
0.18
0.25
0.52
0.39
<10
<10
30
20
n.a.
30
30
3
9
5
70
10
7
<10
6
5
<20
n.a.
n.a.
n.a.
n.a.
700
n.a.
1
1
<10
<20
570
<2
260
2
400 1
n.a.
<30 <10
<10
20
20
30 3900 <5
20 20 1500
<2
<70
40
22
<20
620
420
<5
230
70
180
75
8
40
6 40
<50 <10
<0.19
<0.11
<0.21
<0.46
Salinity wt %
Li
Na
K Mn Fe Cu Zn As Rb
Sr Mo Ag Sn Cs Ba La Ce
W
Tl
Pb Au
NaCl equiv (ppm) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
LA-ICP-MS results of fluid inclusion assemblages shown in Figure 8; each line represents averages and 1s standard deviations from an assemblage with several inclusions of identical phase proportions. With the listed elements
some additional elements were analyzed such as Ca, Mg, Al, Ti, B, Bi, Cl, and Sb, but these numbers were commonly below detection limit or masked by mass interferences, b and v correspond to the coexisting brine and vapor
phase of boiling assemblages.
High-density
vapor inclusion
Type of
inclusion
35
Assemblage
TABLE 6. (Cont.)
1755
1756
20
ULRICH ET AL.
40
15
30
10
20
10
0
30
B 25
20
15
10
5
0
12
C 10
8
6
4
2
0
60
D 50
40
30
20
10
0
25
0
25
20
Opaque-bearing
brine inclusions
15
10
5
0
25
Brine inclusions
20
15
10
5
0
30
25
20
15
10
5
0
20
15
Aqueous inclusions
High-density vapor
inclusions
20
15
10
10
5
0
0 10 20
30 40 50 60 70
5
0
lution or by near-simultaneous vapor and halite disappearance (Fig. 4B). Groups of inclusions (e.g., assemblage 91-93)
homogenizing above 600C were found exclusively in sample
BLA97. The assemblage with the lowest Th(L) (363 42C)
has a salinity of 38 1 wt percent NaCl equiv. The assemblage with the highest salinity (63 4 wt % NaCl equiv) homogenizes by halite dissolution at 524 25C.
Brine inclusion: Most assemblages homogenize to liquid,
and their salinity is near the lower end of the salinity range of
opaque-bearing brine inclusions (Figs. 4A and 5C). Homogenization temperature is distinctly lower compared to the
polyphase and opaque-bearing brine inclusions, mostly
around 340 to 400C. Assemblage 100 shows halite melting
at temperatures much higher than vapor to liquid homogenization temperatures, which may indicate trapping at high
pressure (Bodnar, 1994; Cline and Bodnar, 1994) or some
otherwise unrecognizable postentrapment modification. The
assemblage (104) with the lowest salinity (37 3 wt % NaCl
equiv) has the highest homogenization temperature of 671
6C, whereas the assemblage (101) with the highest salinity
(42 4 wt % NaCl equiv) homogenizes at 387 43C.
Aqueous inclusions: Within a few groups of simple twophase inclusions, hydrohalite was observed as the last melting
phase in individual inclusions (assemblages 5, 5a, 22, Fig. 4A).
0361-0128/98/000/000-00 $6.00
1756
1400
sample BLA 97
other samples
1300
117: boiling
assemblage
1200
boiling
assemblages
92
800C
91
minimum P estimate
104
93
1100
700C
"vapor"
"liquid"
pressure (bars)
pressure (bars)
1000
113
68
900
114
600C
66
800
700
44
45/46
550C
43
115
67
47
117
61
500C
600
500
critical curve
57
450C
400
32
33
300
400C
111
35
100
20
0
1
21
25
73
106
V+NaCl
Cl
101
100
Na
108
62
V+
31
107
116
112
109
L+
40
59
58
54
41/42
200
110
1 0
50
100
wt%
wt% NaCl
NaClequiv
equiv
FIG. 6. Phase diagram of the system NaCl-H2O (Sourirajan and Kennedy, 1962; Urusova, 1975; Bodnar et al., 1985),
showing all boiling assemblages and single-phase assemblages analyzed by LA-ICP-MS. Circles describe the P-T-X variation
of assemblages from sample BLA97, and squares represent other samples from the main mineralized porphyries. Filled labels indicate boiling assemblages (numbers underlined) and open symbols show lower limits for pressure estimates based on
brine-only assemblages. The salinity and homogenization temperature data of the vapor-rich inclusion assemblages have
larger errors due to the underestimation of homogenization temperatures and possible overestimation of the salinity due to
coentrapment of minor liquid. For example, assemblage 35 must have been trapped at pressures greater than 480 bars in the
vapor field.
0361-0128/98/000/000-00 $6.00
1757
1757
1758
ULRICH ET AL.
(9193, 104). Slightly lower minimum pressures are estimated for high-temperature polyphase brine inclusions that
fall close to the 700C isotherm on which the high-temperature boiling assemblages plot. In contrast, low-temperature
assemblages ( 500C) of the different inclusion types give
minimum pressures over the range of 400 to below 100 bars.
Several assemblages consistently show homogenization by
halite melting, and in some assemblages, individual inclusions
homogenize by liquid or by halite melting. Homogenization
by halite dissolution has been interpreted to indicate entrapment of a halite-saturated hydrothermal brine (Eastoe, 1978;
Cloke and Kesler, 1979; Wilson et al., 1980), homogeneous
trapping at high pressures (Bodnar, 1994; Cline and Bodnar,
1994), or postentrapment H2O loss or volume shrinkage
(Sterner et al., 1988). Halite-homogenizing inclusions at
Alumbrera never occur on boiling trails, which would be clear
evidence for postentrapment modification (Audtat and Gnther, 1999). The analyzed fluid inclusion assemblages showed
no petrographic evidence of postentrapment disturbance
(with the possible exception of assemblage 100). We therefore suggest that the halite-homogenizing inclusion assemblages record the entrapment of a single-phase brine, probably not halite saturated, at pressures well above the
liquid-vapor phase boundary (Bodnar, 1994; Cline and Bodnar, 1994). Minimum pressures can be derived for this type of
assemblage if the salinity is around 40 wt percent NaCl equiv,
where experimental isochore data are available (Bodnar,
1994). Two assemblages that homogenize by halite melting
(62, 100) give unreasonably high pressures using the calculation approach of Bodnar (1994). Assemblage 100, although
within the salinity range of the experimental data, gives pressures of around 2.8 kbars due to the large difference between
vapor homogenization and halite dissolution, but the microthermometric data vary over a large range, probably indicating postentrapment disturbance in this case. In the following plots, this assemblage is grouped next to assemblage (101)
of otherwise similar inclusions in the same sample. Assemblage 62 indicates a minimum pressure of 1,135 bars, but the
extrapolation of the experimental data to such high salinities
(70 wt % NaCl equiv) and the known deviation from the
NaCl-H2O model system may lead to errors in the pressure
estimate. When the final homogenization temperature and
the salinity are plotted, this assemblage falls inside the halitesaturated field at ~380 bars (Fig. 6).
Table 5 summarizes the main observations of the depositscale distribution and the microthermometric characteristics
of the fluid inclusion assemblages. Even though it is not possible to document the entire fluid history in time at any point
in the deposit, a generalized fluid evolution can be deduced
on the assumption that each intrusion and its fluid pulse (including the Quartz-Eye Porphyry) followed a similar range of
P-T-XNaCl paths. Significant salinity and density variations of
fluids present during quartz-magnetite and potassic alteration
and probably the initial stages of copper deposition can be explained by a P-T path of general cooling and decompression
of one magmatic fluid. The highest pressure fluids trapped
above 600C are interpreted as the earliest inclusion assemblages. Among these, there is a trend from nonboiling brines
with ~50 wt percent NaCl equiv toward even higher salinity,
essentially following a high-temperature isotherm of the
0361-0128/98/000/000-00 $6.00
1758
1759
100
F=27
Th L= 720C
P= 680 bars
10
Fe
Sn
Ti
Zn
100
Pb
10
Li
Sr
Tl
Cs
Bi
Ce
Ag
Ce
Assemblage 117
La
0.1
0.1
100
La
10
100
0.1
0.1
10
Rb
115
100
F=7
Th L= 470C
P= 320 bars
10
100
10
Ba
Ag
Sb Cs
Mo
Bi
Tl
Mn
Zn
Pb
Sr
Rb
Fe
Na
Cu
Mn
Ba
F=8
Na
Cu
0.1
Th L= 720C
P= 750 bars
0.1
100
10
Th L= 720C
P= 900 bars
F=1
Na
Na
K
Cu
Ti
0.1
Fe
Cu
Mn
La
100
Pb
Rb
Rb
Ba
Cs
Ce
TI
0.1
0.1
10
Zn
Sr
Cs
Bi
Ag Bi
Pb
Ba
Li
Sr
Mn
Zn
10
Fe
Tl
116
100
0.1
100
10
114
0.1
10
100
0.1
100
10
100
Th L= 397C
P= 180 bars
10
F=10
Th L= 448C
P= 270 bars
F=2
Fe
K Na
Cu
0.1
Na
K
Fe
Mn
100
Ag
Mo
Ce
Cs
Mo
Sr Ba
Rb
Bi
Ag
1
106
0.1
0.1
10
Cu
Zn
Pb
Tl
10
Ti
100
0.1
10
100
0.1
Sr
Tl Ba
Li
Ce
La
Cs
10
100
Mn
Zn
Pb
Rb
112
0.1
10
1759
100
1760
ULRICH ET AL.
80
70
60
salinity
1600
1400
1200
50
1000
40
800
Th
30
20
600
400
P
BLA 97: opaque-bearing
and brine inclusions
10
200
Other samples
100
10
1
0.1
NaCl eq.
Na
Mn
Zn
Pb
Rb
100
10
Cs
Tl
1
0.1
100
10
C
Fe
K
1
Ba
Cu
0.1
100
10 Sr
Mo
Au
0.1
1760
et al., 1999). Limits of detection as low as 0.1 ppm Au in 25m inclusions were determined, corresponding to a total
mass of about 1015g Au per inclusion (Ulrich et al., 1999).
Detection limits (calculated from the standard deviation of
background intensity; Gnther et al., 1998, 1999) vary depending on inclusion volume and signal length, and many Au
analyses are close to the limit of detection. Typical uncertainties of 20 percent are estimated from analyses of several microthermometrically identical inclusions in one assemblage,
but they increase for small inclusions (<10 m) and element
concentrations near the detection limit. For the low-density
vapor inclusions in boiling assemblages, only poorly determined minimum concentrations can be given, because the
LA-ICP-MS signals had to be referenced to the theoretical
NaCl concentration of the pure vapor phase estimated from
the NaClH2O phase diagram, ignoring the likelihood of coentrapment of some saline liquid.
Element distribution between brine and vapor
The fluid composition was analyzed on the same assemblages that were used to define the P-T-XNaCl conditions in
the system. These assemblages cover a wide range of Th,
salinity, and density. In boiling assemblages both inclusion
types (liquid- and vapor-rich) were analyzed individually to
explore the fractionation of the different elements between
coexisting fluid phases. Elements including K, Na, Fe, Mn,
Pb, Zn, Rb, Sr, Ba, Cs, Bi, and Ce, and Tl are concentrated
in the liquid phase where they lie within errors on a parallel
array to the line of equal concentrations in both inclusion
types (Fig. 7). Cu, on the other hand, is always shifted toward
the line of equal concentrations or lies above (assemblage
117), i.e., fractionates into the vapor phase relative to the
other metals or even in terms of absolute concentration. The
number indicated in each plot of Figure 7 reports the minimum degree of Cu fractionation between vapor and liquid for
each boiling assemblage using the following ratio (Heinrich et
al., 1999):
CuV/MV
F =
,
CuL/ML
(1)
where Cu and M represent the concentrations of Cu and average concentrations of liquid-partitioning metals, M (Na, K,
Fe, Mn, Zn, Rb, Cs, Pb) in the superscripted fluid phases.
These values are minimum estimates for the actual exchange
constant for Cu between the two end-member fluids. Minor
coentrapment of liquid in the vapor inclusions is most likely
and probably contributes to the near-linear distribution of all
other elements in Figure 7. However, by normalizing the distribution factor with M, the value of F is independent of any
systematic errors due to the internal standardization of the
analyses using Na. Preferential fractionation of Cu into the
vapor phase was suggested and shown for other deposits
(Heinrich et al., 1992, 1999) and is supported by the high Cu
concentrations generally found in high- and low-density vapor
inclusions at Alumbrera, although they do not always demonstrably coexist with a liquid phase. The highest Cu concentration is 3.3 1.2 wt percent Cu, measured in a high-density
vapor assemblage of sample BLA97, which is one order of
magnitude higher than the average Cu concentrations of the
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polyphase brine inclusions (Table 6). Gold was below the detection limit of around 0.5 ppm even in the best signals from
low- and high-density vapor inclusions.
Chemical composition of liquid-rich inclusions
The compositions of the brine and aqueous inclusions, averaged for all analyzed inclusions in each assemblage, are
shown in Figure 8 and Table 6. The assemblages from sample
BLA97 are separated on the left side of the diagram, and all
assemblages are sorted according to a general sequence of decreasing temperature, pressure, and interpreted petrographic
timing. Based on the mineralization and alteration geochemistry of the deposit (Ulrich and Heinrich, 2001) the analyzed
elements are grouped into nonreactive elements (Fig. 8B)
and reactive elements (Fig. 8C). The nonreactive elements
include Cl (not plotted), Na, Mn, Pb, Zn, Rb, Tl, and Cs.
Their concentration trends in the halite-saturated assemblages are parallel to each other and to the total salinity of the
fluid across all samples. These highly soluble elements are effectively conserved and maintain their initial magmatic ratios
in the fluid, as they are transported through the deposit without significant mass transfer by fluid-rock reactions or mineral precipitation. The concentrations of all these elements
remain high in all brine types irrespective of significant variations in pressure and temperature, indicating a common
parentage of the fluid salinity from a magmatic source. Near
the low-temperature end of the trend, the concentration of all
nonreactive elements decreases rapidly, in parallel with the
total fluid salinity, probably indicating late dilution of the
magmatic brine with a low-salinity aqueous fluid.
The reactive elements include K, Fe, Cu, Mo, Au, Sr, and
Ba, whose concentrations vary relative to those of the nonreactive elements and the total salinity as a result of fluid-rock
reaction and mineral precipitation. With the exception of the
very earliest and hottest assemblages in sample BLA97, all
polyphase and opaque-bearing brine inclusions have approximately constant and high concentrations of Cu (avg 0.33 wt
%, range 0.051.0 wt %) as well as Fe and K. However, as the
temperature reaches 400C or less, there is a dramatic drop
in the concentration of Cu (and to a lesser extent Fe and K),
while the salinity and the concentration of all nonreactive elements remain constant and high. This drop in Cu is petrographically reflected by the disappearance of chalcopyrite
daughter crystals (brine inclusion assemblages 100, 101).
Concurrent with the Cu and Fe decrease in the fluid, K is reduced, whereas Ba and Sr are increasing in the fluid. The
possibly earliest high-temperature brine assemblages in sample BLA97 do not match this general trend and were singled
out on the left side of Figure 8 (assemblages 104, 93, 91, 92).
They show much lower Cu concentrations despite very high
temperature and pressure of entrapment and otherwise similar composition to other opaque-bearing brine inclusions.
Molybdenum concentrations in the high-temperature input
fluid are about 100 ppm and drop below the relatively poor
detection limit at the stage where the Cu concentration decreases sharply.
Limited data for the Au concentrations in high-temperature polyphase brine inclusions (assemblages 6668) indicate
an average Au content of the magmatic brine of 0.55 ppm
(range 0.21.4 ppm; Table 6, Fig. 8). Figure 9 shows all Au
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ULRICH ET AL.
10
Au/Cu=1.2* 10-4
inferred
input fluid
ore samples
bulk ore
0.1
Cu loss
polyphase
brine inclusions
0.01
0.01
0.1
10
Au (ppm)
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Measured
18O
( SMOW)
T(C)
Calculated fluid1
D
18O
( SMOW)
( SMOW)
Igneous minerals
Northwest Porphyry
LP
Bio
-109.8 (0.8)
Qtz
9.2 (0.1)
700
-65.9 (2.4)
8.5 (0.4)
-65.4 (9)
9.9 (0.9)
8.3 (0.3)
-65.4 (9)
49-61.4/357m
Qtz
Mag
10.6 (0.1)
3.1
700
Qtz
Mag
10.5 (0.04)
2.8
700
9.9 (0.9)
8.0 (0.3)
WR (bio)
-68.3 (2.7)
Qtz
8.5 (0.2)
500
-29.8 (4.7)
5.3 (0.9)
49.2-46.3/452m
WR (bio)
-80.1 (3.8)
Qtz
9.7 (0.05)
500
-41.7 (4.7)
6.5 (0.9)
Qtz
11.3 (0.2)
500
-55 (22.8)
Qtz
9.2 (0.2)
500
-55
6.1 (0.9)
-71.1
Qtz
10.3 (0.1)
300
-52.1 (10)
3.4 (1.8)
BLA 97
43-47.1/195m
Fluid incl.
8.1 (1.2)
57.5-60/51m
WR (ser)
-73.3 (0.2)
Qtz
10.7 (0.2)
300
-54.3 (10)
3.9 (1.8)
55.5-60/192m
Fluid incl.
-52
Qtz
8.3 (0.08)
300
-52
1.4 (1.8)
38-49/97m
Fluid incl.
-79 (19.5)
Qtz
10.2 (0.01)
300
-79
3.3 (1.8)
-76.6 (0.8)
Ab
10.6 (0.1)
300
-41.6 (5)
4.7 (1.7)
Chl
-78.3
Ab
9.9 (0.1)
300
-43.3 (5)
4.0 (1.7)
Bio
-79.4 (6.7)
Bio
7.4 (0.04)
350
-44.4 (5)
9.4 (0.1)
37-49/275m
Bio
-90.1 (1.6)
Bio
6.5 (0.04)
350
-55.7 (5)
8.5 (0.1)
37-49/275m
WR (bio)
-83.1 (1.8)
WR (bio)
6.5 (0.04)
350
-48.1 (5)
8.5 (0.1)
-69.3 (15.3)
Qtz
10.7 (0.2)
300
-50.3
3.9 (1.8)
-30
-5
-70 (3)
0.1 (3.2)
Fluid incl.
-70 (3)
Qtz
11.70
200
Abbreviations: bio = biotite, chl = chlorite, mag = magnetite, qtz = quartz, ser = sericite, WR = whole rock
Measured 18O and D of alteration minerals and the calculated isotopic signature of the fluids in equilibrium with the rock; the numbers in brackets of
the measured isotopic signature correspond to 1 and the numbers in brackets for the calculated signature indicates the variation of the isotopic signature for
temperatures of 50C above and below the cited temperature
1Fractionation factors used for the calculation of the isotopic fluid signature in the respective temperature interval are from Bottinga and Javoy (1973),
Matsuhisa et al. (1979), and Javoy (1977) for the oxygen isotopes and from Suzuoki and Epstein (1976) and Graham et al. (1987) for the hydrogen isotopes;
since at low temperatures the experimental data are rare, the fractionation factors were taken from the extrapolated curves from the diagram of Taylor (1997)
2Average of present-day measurements of meteoric water at Salta, Argentina; see text for explanation
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ULRICH ET AL.
feldspardestructive
quartz-magnetite
-60
quartz/sericite
quartz/biotite
-80
albite/
chlorite
biotite/biotite
chlorite-epidote
-100
Northwest Porphyry
-120
quartz/biotite
A
10
18O
12
-20
potassic
(porphyry)
500C
"present-day
meteoric water"
-30
potassic
(wall rock)
350C
chlorite-epidote
300C
-40
feldspardestructive
300C
-50
-60
-70
quartz-magnetite
700C
Northwest
Porphyry
700C
primary
magmatic water
-80
B
-90
-10
-5
10
15
Fig 10. Isotopic signatures of the fluids associated with the magmatic and the alteration stages. A. Analyses of mineral
pairs that were analyzed for hydrogen and oxygen, respectively. B. Calculated isotopic signature of fluids at the indicated
temperatures for the different alteration zones and the Northwest Porphyry. Closed symbols are calculated values, open symbols indicate fluid inclusion extracts for hydrogen. The white triangle is from a nearby epithermal quartz vein and contained
fluid inclusions. The inclined bars represent the variation of fluid composition as a result of a temperature uncertainty of
50C. See text for discussion.
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large range of the values directly obtained from bulk fluid inclusion extracts (D = 39 to 71), which represent unknown proportions of vapor and brine inclusions in the samples. The calculated fluid in equilibrium with biotite (D =
42 and 30) corresponds more closely to equilibrium with
the vapor phase. With the limited amount of analyses we cannot decide whether this is due to reequilibration of the biotite
with the vapor phase, due inadequately corrected effects of
biotite composition, or due to variations in the initial magmatic fluid composition.
The calculated fluid in equilibrium with the secondary biotite in the andesitic wall rock, assuming a formation temperature of 350C, lies within and above the magmatic water box
but is shifted to the right of the samples of the potassic alteration in the porphyries (Fig. 10B). This difference might be
due to incipient feldspar-destructive overprint of the porphyry samples or due to the uncertainty in the fractionation
factor of biotite at 350C.
Propylitic (chlorite-epidote) alteration: The fluid for the
chlorite-epidote alteration is calculated with an estimated D
fractionation factor of 35 per mil for chlorite at 300C. The
D values of 41 to 44 per mil are in the same range as the
potassic alteration fluid, but the oxygen isotope signature
(based on coexisting albite) is shifted to lighter values (45)
and plots left of the magmatic water box. No salt correction
was applied for the calculation, assuming that a low-salinity
fluid (aqueous inclusions) was related to this alteration stage.
Feldspar-destructive alteration (sericite and/or clay and
late vein quartz): Isotopic fluid compositions were based on a
temperature of 300C and a poorly constrained fractionation
factor of D = 19 per mil, considering the mixture of muscovite and clay minerals in this alteration. The fluid signatures
obtained from quartz and sheet silicate extracts are around
D = 53 per mil and 18O = 3.7 per mil. Three hydrogen
analyses of the low-salinity aqueous and vapor-rich inclusions
extracted from two veins with strong feldspar-destructive
overprint have poorly reproducible D values of 52 to 79
per mil, and yield 18O values of ~1.4 to 3.3 per mil for the
fluid coexisting with quartz. The consistent shift toward lower
oxygen values is more prominent than in the fluid associated
with the chlorite-epidote alteration and indicates either a
minor meteoric water component or intense exchange of
magmatic water with rocks at lower temperatures (Fig. 10B).
Discussion
The combination of P-T-XNaCl data (Fig. 6), the fluid compositional variations determined by LA-ICP-MS (Fig. 8), and
the constraints from stable isotopes (Fig. 10) allow a tentative
but consistent reconstruction of the hydrothermal processes
that contributed to the formation of the porphyry Cu-Au deposit at Bajo de la Alumbrera.
Input fluid and magmatic source
The most likely parental ore fluid is recorded by numerous
assemblages of polyphase and opaque-bearing brine inclusions
associated with quartz-magnetite and potassic alteration in all
mineralized porphyries. This fluid was hot (700C), locally
trapped at high pressure, and of dominantly magmatic origin.
It may or may not have boiled during its ascent from an underlying magma chamber, but it intersected the two-phase
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ULRICH ET AL.
curve shortly after arriving at the deposit area. Its salinity was
52 to 58 wt percent NaCl equiv or a little less if the highest
pressure boiling assemblage (113) was already modified by
some vapor loss. This fluid contained similar concentrations
of Na (~16 wt %), K (~12 wt %), and Fe (~8 wt %) and high
copper concentrations (up to 1 wt %). The fluid was also gold
rich (up to 1.4 ppm Au), with an Au/Cu ratio (encircled analyses in Fig. 9) that closely matches the bulk Au/Cu ratio of the
entire economic orebody. Despite systematic search, no inclusions of intermediate salinity and near-critical density were
observed at Alumbrerain contrast, for example, to the porphyry stage at Butte, Montana (Roedder, 1971), and suggestions that such supercritical fluids might be the most likely
parental ore fluids in other porphyries (Bodnar and Cline,
1991; Bodnar, 1998).
Thermodynamic modeling (Cline and Bodnar, 1991; Cline,
1995) based on experimental data (e.g., Kilinc and Burnham,
1972; Candela and Piccoli, 1995) indicates that initial fluid
saturation from a Cl-OH-bearing calc-alkaline magma at
pressures above 1 kbar leads to preferential partitioning of Cl
into the first exsolving fluid phase. This permits efficient extraction of Cl-complexed metals (Cu and probably Au) into an
early-exsolving fraction of high-salinity fluid. The high salinity, the high metal content, and the highest minimum pressures of 1.3 kbars recorded by the fluid inclusions at Alumbrera are in excellent agreement with such a source process
operating in a magma chamber located a few kilometers
below the present exposure level. Ulrich et al. (1999) estimated the minimum volume of this inferred magma reservoir
as ~100 km3, based on a comparison of the gold concentration
in normal magmas with the known mass of gold in the deposit. The extreme salinity and very high metal concentration
of this early fluid fraction implies that a normal calc-alkaline
magma with a typical water content of 4 wt percent, as required for amphibole crystallization (Naney, 1983), would
have to lose a significant fraction of lower salinity fluid after
the main mineralization stage. This low-salinity fluid might be
recorded in the extensive feldspar-destructive alteration that
postdates ore formation at Alumbrera and could be evolved
from a collapsing magmatic plume that interacts with wall
rock at low temperatures and minor meteoric water (Hedenquist and Shinohara, 1997). However, the alternative possibility exists that a special magma with an unusually high Cl/OH
ratio, or with an exceptionally high Au/Cu ratio and Au content (>2 ppb, Connors et al., 1993) acted as the fluid source
for the Alumbrera deposit.
Ore fluid evolution
The fluid evolution recorded by sample BLA97 and samples from the mineralized P2 and Early P3 Porphyries (Fig. 6)
indicates an initial trend of decreasing pressure at high temperatures (>650C), with brine salinities increasing from 50
to over 70 wt percent NaCl equiv. This is a result of vapor phase
separation, as indicated by numerous boiling assemblages of simultaneously trapped brine and vapor inclusions in a single
microfracture. Variants in the exact P-T evolution of individual fluid packets are recorded by different homogenization
behavior of inclusion assemblages, including homogenization
by halite dissolution at pressures well above the two-phase
envelope (Figs. 4B, 6). These variants in P-T evolution and
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the constantly high salinity with fixed proportions of the nonreactive elements despite the Cu decrease in the fluids. The
fluid chemical evidence for cooling as the prime cause for
copper sulfide deposition is in perfect agreement with the
thermodynamic analysis of the Sungun porphyry by
Hezarkhani et al. (1999), who used recent experimental data
on Cu complex stability to confirm the earlier conclusion by
Barnes (1979) that fluid cooling to relatively low temperatures is the key to chalcopyrite precipitation in porphyry copper deposits. The ore grades of gold and copper at Bajo de la
Alumbrera are controlled by the magmatic fluid source and
the relatively low temperature coprecipitation of chalcopyrite
and native gold, rather than by the mineral chemistry of auriferous bornite precipitated at high temperature as suggested in general by Simon et al. (2000).
The concentration variations of reactive elements in the
fluids permit a direct estimate of the mass transfer associated
with the ore deposition process. By comparing the chemical
concentration changes in the fluid with the gains and losses
associated with the alteration of the rocks, an estimate of the
integrated fluid/rock ratio associated with potassic alteration
and Cu mineralization can be calculated. For each of the elements, Cu, Fe, K, Ba and Sr, the concentration decrease or
increase from the early ore-bearing polyphase brine inclusions to the later simple brine inclusions (the spent ore fluid)
was divided by the respective gains or losses of the Early P3
Porphyry (Ulrich and Heinrich, 2001, eq. 3). The resulting ratios vary from 1.5 (Cu) to 0.1 (Fe), but gains by the rock always correspond to metal losses by the fluid and vice versa for
all reactive elements. A variation within an order of magnitude is well within the uncertainty of such estimates, which
assume that a single sample set is representative for a bulkrock mass exceeding 107 t. The best estimate is the one based
on Cu, where approximately 3.3 g Cu/kg fluid are precipitated
to obtain an orebody with an average grade of 0.5 wt percent
or 5 g Cu/kg ore. This implies a bulk fluid/rock ratio of 1.5,
which illustrates that a comparatively modest amount of
highly metal charged magmatic fluid is sufficient to cause the
major mass transfer associated with potassic alteration and
porphyry copper mineralization. Nevertheless, a high degree
of fluid focusing from a large magmatic source volume to the
porphyry stock is required, as shown by comparing the
fluid/rock ratio in the deposit volume (1.5 or 150%) with the
proportion of magmatic brine that can be exsolved from the
crystallizing source pluton: at most a few percent, but probably much less, considering the unusually high salinity and
high Au concentration of the brine (Ulrich et al., 1999).
While the precipitation mechanism for Au and Cu is highly
efficient and nearly complete, ore metal deposition is also
highly selective. The average Mo/Cu ratio in the input fluid
(~0.03) is significantly higher than the average Mo/Cu concentration ratio in the orebody (0.005). This is consistent with
petrographic evidence and grade distribution data (MIM,
unpub. data), indicating that a significant fraction of the Mo
is transported through the main ore shell (economically
defined by the Cu and Au grades) and dispersed into the
subeconomic outer fringes of the magmatic-hydrothermal
system. Pb and Zn occur in equally high concentrations in the
magmatic fluid as Cu, but they behave as nonreactive elements and are not precipitated within the orebody volume.
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ULRICH ET AL.
fluid inclusion compositions in complex magmatic-hydrothermal systems. Extensive data for ore metal concentrations in the
evolving fluids has provided new insights about the source of
the metals, their transport, and the mechanisms of their precipitation. Our study also illustrates the potential of future applications of this microanalytical technique in mineral exploration.
The geologic study of Bajo de la Alumbrera showed a complex evolution of intrusive and veining events but a comparatively simple zonation of wall-rock alteration and ore-grade
distribution. The fluid inclusion record is dominated by brine
inclusions of relatively constant composition throughout all
stages of quartz veining and high-temperature alteration. Ore
metal concentrations remained high, despite large pressure
and temperature fluctuations, resulting in variable fluid densities of boiling and nonboiling brines. Cu and Au were precipitated upon cooling of the brines below a saturation temperature near 400C, while other metals like Pb and Zn were
flushed through the Cu-Au-mineralized vein stockwork without ever reaching saturation. Inclusions of Pb-Zn-rich but
Cu-depleted (spent) ore fluid could provide a useful indicator
for the proximity of an undiscovered Cu ( Au Mo) deposit
during exploration of poorly exposed grounds.
Fluid cooling as the prime factor controlling Cu-Au deposition implies that the bulk hypogene ore grade of a porphyrytype orebody is mainly controlled by the thermal structure of
the fluid-flow system. A large and rich deposit will form
where a high flux of metal-rich brine is focused from a major
magma reservoir through a restricted volume of highly permeable rock (i.e., the fractured porphyry neck) and is at the
same time efficiently cooled through the critical temperature
interval of ore mineral saturation. Efficient cooling probably
requires stable convection of external fluids around the magmatic fluid plume (ideally without direct mixing and dilution
of the magmatic brine). Vapor phase separation may have an
additional effect on the heat budget, but a site of productive
porphyry copper mineralization is probably characterized by
only minor net loss of vapor and the relatively volatile ore
metals (As, Sb, Cu, Au) to an overlying epithermal environment. Fluid-flow patterns, heat budget, and degree of brinevapor separation will be primarily controlled by the pressure
evolution and, thus, by the permeability structure between
the magma chamber and the surface.
The near-constant composition of preore stage brines provides information about the igneous fluid source, an inferred
subjacent magma chamber of at least 100-km3 size in the case
of Bajo de la Alumbrera and other deposits of similar size.
Orebody composition is determined by the Cu/Au ratio of the
mineralizing ore fluid, and this fluid composition is in turn
controlled by the magmatic fluid source. A future challenge
therefore lies in the development of practical techniques and
fundamental understanding to read the record of ordinary igneous rocks, notably the composition of silicate melts inclusions in unmineralized intrusions and associated volcanic
rocks. This may become a valuable source of information to
identify prospective igneous complexes and to determine the
productive fluid-generating stages within them.
Acknowledgments
We are grateful to MIM Exploration and Minera Alumbrera for generous financial, logistic, and scientific support of
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Bowman, J.R., Parry, W.T., Kropp, W.P., and Kruer, S.A., 1987, Chemical and
isotopic evolution of hydrothermal solutions at Bingham, Utah: ECONOMIC
GEOLOGY, v. 82, p. 395428.
Burnham, C.W., and Ohmoto, H., 1980, Late-stage processes of felsic magmatism: Mining Geology Special Issue 8, p. 113.
Candela, P.A., and Holland, H.D., 1986, A mass transfer model for copper
and molybdenum in magmatic hydrothermal systems: The origin of porphyry-type ore deposits: ECONOMIC GEOLOGY, v. 81, p. 119.
Candela, P.A., and Piccoli, P.M., 1995, Model ore-metal partitioning from
melts into vapor and vapor/brine mixtures: Mineralogical Association of
Canada Short Course Series 23, p. 101127.
Chivas, A.R., and Wilkins, R.W.T., 1977, Fluid inclusion studies in relation to
hydrothermal alteration and mineralization at the Koloula porphyry copper
prospect, Guadalcanal: ECONOMIC GEOLOGY, v. 72, p. 153169.
Cline, J.S., 1995, Genesis of porphyry copper deposits: The behavior of
water, chloride, and copper in crystallizing melts: Arizona Geological Society Digest, v. 20, p. 6982.
Cline, J.S., and Bodnar, R.J., 1991, Can economic porphyry copper mineralization be generated by a typical calc-alkaline melt?: Journal of Geophysical Research, v. 96, p. 81138126.
1994, Direct evolution of brine from a crystallizing silicic melt at the
Questa, New Mexico, molybdenum deposit: ECONOMIC GEOLOGY, v. 89, p.
17801802.
Cloke, P.L., and Kesler, S.E., 1979, The halite trend in hydrothermal solutions: ECONOMIC GEOLOGY, v. 74, p. 18231831.
Connors, K.A., Noble, D.C., Bussey, S.D., and Weiss, S.I., 1993, Initial gold
contents of silicic volcanic rocks: Bearing on the behavior of gold in magmatic systems: Geology, v. 21, p. 937940.
Damman, A.R., Kras, M.S., Touret, L.R.J., Rieffe, C.E., Kramer, A.L.M., Vis,
D.R., and Pintea, I., 1996, PIXE and SEM analyses of fluid inclusions in
quartz crystals from the K-alteration zone of the Rosia Poieni porphyry-Cu
deposit, Apuseni Mountains, Rumania: European Journal of Mineralogy, v.
8, p. 10811096.
Diamond, l.W., Marshall, D.D., Jackman, J.A., and Skippen, G.B., 1990, Elemental analysis of individual fluid inclusions in minerals by secondary ion
mass spectrometry (SIMS): Application to cation ratios of fluid inclusions
in an Archaean mesothermal gold-quartz vein: Geochimica et Cosmochimica Acta, v. 54, p. 545552.
Dilles, J.H., Solomon, G.C., Taylor, H.P., Jr., and Einaudi, M.T., 1992, Oxygen and hydrogen isotope characteristics of hydrothermal alteration at the
Ann-Mason porphyry copper deposit, Yerington, Nevada: ECONOMIC GEOLOGY, v. 87, p. 4463.
Dobson, P.F., Epstein, S., and Stolper, E.M., 1989, Hydrogen isotope fractionation between coexisting vapor and silicate glasses and melts at low
pressure: Geochimica et Cosmochimica Acta, v. 53, p. 27232730.
Downs, W.F., Touysinhthiphoneeaxy, Y., and Deines, P., 1981, A direct determination of the oxygen isotope fractionation of quartz and magnetite at
600 and 800C and 5 kbar: Geochimica et Cosmochimica Acta, v. 45, p.
20652072.
Eastoe, C.J., 1978, A fluid inclusion study of the Panguna porphyry copper
deposit Bougainville, Papua New Guinea: ECONOMIC GEOLOGY, v. 73, p.
721748.
1982, Physics and chemistry of the hydrothermal system at the Panguna
porphyry copper deposit, Bougainville, Papua New Guinea: ECONOMIC
GEOLOGY, v. 77, p. 127153.
Etminan, H., 1977, Le porphyre cuprifere de Sar Cheshmeh (Iran); role des
phases fluides dans les mecanismes d`alteration et de mineralisation: Unpublished Ph.D. thesis, Nancy, Science de la Terre,Universite de Nancy, 249 p.
Gammons, C.H., and Williams-Jones, A.E., 1997, Chemical mobility of gold
in the porphyry-epithermal environment: ECONOMIC GEOLOGY, v. 92, p.
4559.
Giletti, B.J., 1985, The nature of oxygen transport within minerals in the
presence of hydrothermal water and the role of diffusion: Chemical Geology, v. 53, p. 197206.
1986, Diffusion effects on oxygen isotope temperatures of slowly cooled
igneous and metamorphic rocks: Earth and Planetary Science Letters, v.
77, p. 218228.
Gilg, H.A., and Sheppard, S.M.F., 1996, Hydrogen isotope fractionation between kaolinite and water revisited: Geochimica et Cosmochimica Acta, v.
60, p. 529533.
Goldstein, R.H., and Reynolds, T.J., 1994, Systematics of fluid inclusions in
diagenetic minerals: Society for Sedimentary Geology Short Course 31,
199 p.
1769
1770
ULRICH ET AL.
Graham, C.M., Viglino, J.A., and Harmon, R.S., 1987, Experimental study of
hydrogen-isotope exchange between aluminous chlorite and water and of
hydrogen diffusion in chlorite: American Mineralogist, v. 72, p. 566579.
Gnther, D., and Heinrich, C.A., 1999, Enhanced sensitivity in laser ablation
ICP-mass-spectrometry using helium-argon mixtures as aerosol carrier:
Journal of Analytical Atomic Spectroscopy, v. 14, p. 13631368.
Gnther, D., Frischknecht, R., Heinrich, C.A., and Kahlert, H.-J., 1997, Capabilities of an argon fluoride 193 nm Excimer laser for laser ablation inductively coupled plasma mass spectrometry microanalysis of geological
materials: Journal of Analytical Atomic Spectroscopy, v. 12, p. 939944.
Gnther, D., Audtat, A., Frischknecht, R., and Heinrich, C.A., 1998, Quantitative analysis of major, minor and trace elements in fluid inclusions using
laser ablation-inductively coupled plasma-mass spectrometry (LA-ICPMS): Journal of Analytical Atomic Spectroscopy, v. 13, p. 263270.
Gnther, D., Jackson, S.E., and Longerich, H.P., 1999, Laser ablation and
arc/spark solid sample introduction into inductively coupled plasma mass
spectrometers: Spectrochimica Acta, Part B, v. 54, p. 381409.
Hedenquist, J.W., 1995, The ascent of magmatic fluid: Discharge versus mineralization: Mineralogical Association of Canada Short Course Series 23, p.
263289.
Hedenquist, J.W., and Richards, J.P., 1998, The influence of geochemical
techniques on the development of genetic models for porphyry copper deposits: Reviews in Economic Geology, v. 10, p. 235256.
Hedenquist, J.W., and Shinohara, H., 1997, K-silicate- to sericite-stage transition in porphyry Cu deposits; collapse of magmatic plume, or overprint by
meteoric water? [abs.]: Geological Society of America Abstracts with Programs v. 29, p. 359.
Hedenquist, J.W., Arribas, A., Jr., and Reynolds, T.J., 1998, Evolution of an
intrusion-centered hydrothermal system: Far Southeast-Lepanto porphyry
and epithermal Cu-Au deposits, Philippines: ECONOMIC GEOLOGY, v. 93, p.
373404.
Heinrich, C., 1990, The chemistry of hydrothermal tin (-tungsten) ore deposition: ECONOMIC GEOLOGY, v. 85, p. 457481.
Heinrich, C.A., Ryan, C.G., Mernagh, T.P., and Eadington, P.J., 1992,
Segregation of ore metals between magmatic brine and vapor: A fluid
inclusion study using PIXE microanalysis: ECONOMIC GEOLOGY, v. 87, p.
15661583.
Heinrich, C.A., Gnther, D., Audtat, A., Ulrich, T., and Frischknecht, R.,
1999, Metal fractionation between magmatic brine and vapor, determined
by micro-analysis of fluid inclusions: Geology, v. 27, p. 755758.
Heithersay, P.S., and Walshe, J.L., 1995, Endeavour 26 North: A porphyry
copper-gold deposit in the Late Ordovician, Shoshonitic Goonumbla Volcanic Complex, New South Wales, Australia: ECONOMIC GEOLOGY, v. 90, p.
15061532.
Hemley, J.J., Cygan, G.L., Fein, J.B., Robinson, G.R., Jr., and dAngelo,
W.M., 1992, Hydrothermal ore-forming processes in the light of studies in
rock-buffered systems: I. Iron-copper-zinc-lead sulfide solubility relations:
ECONOMIC GEOLOGY, v. 87, p. 122.
Henley, R.W., and McNabb, A., 1978, Magmatic vapor plumes and groundwater interaction in porphyry copper emplacement: ECONOMIC GEOLOGY,
v. 73, p. 120.
Hezarkhani, A., and Williams-Jones, A.E., 1998, Controls of alteration and
mineralization in the Sungun porphyry copper deposit, Iran: Evidence from
fluid inclusions and stable isotopes: ECONOMIC GEOLOGY, v. 93, p. 651670.
Hezarkhani, A., Williams-Jones, A.E., and Gammons, C.H., 1999, Factors
controlling copper solubility and chalcopyrite deposition in the Sungun
porphyry copper deposit, Iran: Mineralium Deposita, v. 34, p. 770783.
Horita, J., Cole, D.R., and Weslowski, D.J., 1995, The activity-composition
relationship of oxygen and hydrogen isotopes in aqueous salt solutions: III.
Vapor-liquid water equilibration of NaCl solutions to 350C: Geochimica et
Cosmochimica Acta, v. 59, p. 11391151.
International Atomic Energy Agency (IAEA), 1999, Global network for isotopes in precipitation database. http://www.iaea.org/programs/ri/gnip/gnipmain.htm
Javoy, M., 1977, Stable isotopes and geothermometry: Journal of the Geological Society of London, v. 133, p. 609636.
John, D.A., 1989, Evolution of hydrothermal fluids in the Park Premier stock,
Central Wasatch Mountains, Utah: ECONOMIC GEOLOGY, v. 84, p. 879902.
Kilinc, I.A., and Burnham, C.W., 1972, Partitioning of chloride between a silicate melt and coexisting aqueous phase from 2 to 8 kilobars: ECONOMIC
GEOLOGY, v. 67, p. 231235.
Lindgren, W., 1905, The copper deposits of the Clifton-Morenci district, Arizona: U.S. Geological Survey Professional Paper, v. 43, 375 p.
0361-0128/98/000/000-00 $6.00
Malvicini, L., and Llambias, E.J., 1963, Mineralogia y origin de los minerales
manganeso y sus asociados en Farallon Negro, Alto de la Blenda y los Viscos, Hualfin, Catamarca: Revista Asociacin Geolgica [Argentina], v. 18, p.
177199.
Matsuhisa, Y., Goldsmith, J.R., and Clayton, R.N., 1979, Oxygen isotopic
fractionation in the system quartz-albite-anorthite-water: Geochimica et
Cosmochimica Acta, v. 43, p. 11311140.
Matthews, A., Goldsmith, J.R., and Clayton, R.N., 1983, Oxygen isotope fractionations involving pyroxenes: The calibration of mineral-pair geothermometers: Geochimica et Cosmochimica Acta, v. 47, p. 631-644.
Mavrogenes, J.A., and Bodnar, R.J., 1994, Hydrogen movement into and out
of fluid inclusions in quartz: Experimental evidence and geological implications: Geochimica et Cosmochimica Acta, v. 58, p. 141148.
Mavrogenes, J.A., Bodnar, R.J., Anderson, A.J., Bajt, S., Sutton, S.R., and
Rivers, M.L., 1995, Assessment of the uncertainties and limitations of
quantitative elemental analysis of individual fluid inclusions using synchrotron X-ray fluorescence (SXRF): Geochimica et Cosmochimica Acta, v. 59,
p. 39873995.
Mndez, V., 1997, Yacimiento Bajo La Alumbrera, Provincia de Catamarca,
Repblica Argentina: Revista de la Asociacin Argentina de Gelogos
Economistas, v. 11, p. 1530.
Naney, M.T., 1983, Phase equilibria of rock-forming ferromagnesian silicates
in granitic systems: American Journal of Science, v. 283, p. 9931033.
Nash, T.J., 1976, Fluid-inclusion petrologydata from porphyry copper deposits and applications to exploration: U.S. Geological Survey Professional
Paper, v. 907- D, p. D1D16.
Oreskes, N., and Einaudi, M.T., 1992, Origin of hydrothermal fluids at
Olympic Dam: Preliminary results from fluid inclusions and stable isotopes: ECONOMIC GEOLOGY, v. 87, p. 6490.
Preece, R.K., III, and Beane, R.E., 1982, Contrasting evolutions of hydrothermal alteration in quartz monzonite and quartz diorite wall rocks at
the Sierrita porphyry copper deposit, Arizona: ECONOMIC GEOLOGY, v. 77,
p. 16211641.
Quan, R.A., Cloke, P.L., and Kesler, S.E., 1987, Chemical analyses of halite
trend inclusions from the Granisle porphyry copper deposit, British Columbia: ECONOMIC GEOLOGY, v. 82, p. 19121930.
Reynolds, T.J., and Beane, R.E., 1985, Evolution of hydrothermal fluid characteristics at the Santa Rita, New Mexico, porphyry copper deposit: ECONOMIC GEOLOGY, v. 80, p. 13281347.
Roedder, E., 1971, Fluid inclusion studies on the porphyry-type ore deposits
at Bingham, Utah, Butte, Montana, and Climax, Colorado: ECONOMIC GEOLOGY, v. 66, p. 98120.
1984, Fluid inclusions: Reviews in Mineralogy, v. 12, 646 p.
Roedder, E., and Bodnar, R.J., 1980, Geologic pressure determinations from
fluid inclusion studies: Annual Review of Earth and Planetary Science, v. 8,
p. 263301.
Rye, R.O., 1993, The evolution of magmatic fluids in the epithermal environment: The stable isotope perspective: ECONOMIC GEOLOGY, v. 88, p. 733752.
Sasso, A.M., and Clark, A.H., 1998, The Faralln Negro group, northwestern
Argentina: Magmatic, hydrothermal and tectonic evolution and implications for Cu-Au metallogeny in the Andean back-arc: Society of Economic
Geologists Newsletter, v. 34, p. 1, 818.
Sheets, R.W., Nesbitt, B.E., and Muehlenbachs, K., 1996, Meteoric water
component in magmatic fluids from porphyry copper mineralization,
Babine Lake area, British Columbia: Geology, v. 24, p. 10911094.
Shepherd, T.J., and Chenery, S.R., 1995, Laser ablation ICP-MS elemental
analysis of individual fluid inclusions: An evaluation study: Geochimica et
Cosmochimica Acta, v. 59, p. 39974007.
Shepherd, T.J., Rankin, A.H., and Alderton, D.H.M., 1985, A practical guide
to fluid inclusion studies: London, Blackie and Son, Ltd., 239 p.
Shinohara, H., and Hedenquist, J.W., 1997, Constraints on magma degassing
beneath the Far Southeast porphyry Cu-Au deposit, Philippines: Journal of
Petrology, v. 38, p. 17411752.
Shmulovich, K.I., Landwehr, D., Simon, K., and Heinrich, W., 1999, Stable
isotope fractionation between liquid and vapour in water-salt systems up to
600C: Chemical Geology, v. 157, p. 343354.
Simon, G., Kesler, S.E., Essense, E.J., and Chryssoulis, S.L., 2000, Gold in
porphyry copper deposits: Experimental determination of the distribution
of gold in the Cu-Fe-S system at 400 to 700C: ECONOMIC GEOLOGY, v. 95,
p. 259270.
Solomon, G.C., 1983, 18O/16O and D/H characteristics of the Ann-Mason
porphyry copper deposit, Yerington, Nevada [abs.]: Geological Society of
America Abstracts with Programs, v. 15, p. 277.
1770
0361-0128/98/000/000-00 $6.00
1771
Ulrich, T., Gnther, D., and Heinrich, C.A., 1999, Gold concentrations of
magmatic brines and the metal budget of porphyry copper deposits: Nature, v. 399, p. 676679.
Urusova, M.A., 1975, Phase equilibria and thermodynamic characteristics of
solutions in the systems NaCl-H2O and NaOH-H2O at 350-550C: Geochemistry International, v. 1974, p. 944950.
Vityk, M.O., and Bodnar, R.J., 1998, Statistical microthermometry of synthetic fluid inclusions in quartz during decompression reequilibration:
Contributions to Mineralogy and Petrology, v. 132, p. 149162.
Wall, V.J., 1997, Bajo de la Alumbrera (Argentina). A world class copper gold
deposit: Revista de la Asociacin Argentina de Gelogos Economistas, v.
11, p. 9293.
Weisbrod, W., 1981, Fluid inclusions in shallow intrusives: Mineralogical Association of Canada Short Course 6, p. 241271.
Wilson, J.W. Jr., Kesler, S.E., Cloke, P.L., and Kelly, W.C., 1980, Fluid inclusion geochemistry of the Granisle and Bell porphyry copper deposits,
British Columbia: ECONOMIC GEOLOGY, v. 75, p. 4561.
Zaluski, G., Nesbitt, B., and Muehlenbachs, K., 1994, Hydrothermal alteration and stable isotope systematics of the Babine porphyry Cu deposits,
British Columbia: Implications for fluid evolution of porphyry systems:
ECONOMIC GEOLOGY, v. 89, p. 15181541.
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APPENDIX 1
Samples Used for the Fluid Inclusion Analyses
The samples are listed according to the different types of
inclusions, except for sample BLA97 where different inclusion assemblages were analyzed from the same sample. The
fluid inclusion assemblages listed in Figures 6 and 8 and Tables 4 and 6 appear in parentheses.
47-53/25 (assemblage 47)
depth: 118 m
depth: 192 m
depth: 523 m
depth: 311 m
depth: 334 m
depth: 315 m
Surface sample
depth: 428 m
depth: 118 m
depth: 353 m
Barren quartz vein in potassically altered Early P3 Porphyry. Some primary biotite in the wall rock is unaltered,
whereas the hornblende is altered to secondary biotite, minor
K feldspar. The quartz vein is coarse grained and about 7 mm
wide. Only one vapor inclusion in the boiling trail could be
measured, all others were of the low-density type.
49-50.1/4 (109)
depth: 357 m
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The veins are between 3 to 6 mm wide. The boiling assemblage consists of polyphase brine coexisting with some highdensity vapor as well as low-density vapor inclusions.
grained quartz vein of about 7-mm width. The boiling assemblage contains mostly low-density vapor inclusions next to the
polyphase brine inclusions.
51-52.2/13 (113)
depth: 242 m
depth: 212 m
P2 or Early P3 Porphyry with coarse-grained quartz-magnetite veins. The magnetite occurs in the center of the veins.
The veins are 4 to 7 mm wide. The boiling assemblage consists
of polyphase brine and mostly low-density vapor inclusions.
depth: 337 m
APPENDIX 2
Description of Samples Used for the Stable Isotope Analyses
LP
49.2-46.3/1-2
depth: 264-265 m
Unaltered porphyry sample with fresh plagioclase, hornblende, and biotite crystals up to 3 mm. Biotite was separated
by handpicking.
49-60/12
57.5-60/7
depth: 93 m
depth: 51 m
49-61.4/3-5
BLA 55
depth: 357 m
depth: 308 m
BLA 97
Strongly altered (feldspar-destructive) Quartz-Eye Porphyry with barren quartz veins and later pyrite infill. The vein
quartz was analyzed for its oxygen isotope signature and hydrogen isotopes were analyzed in fluid inclusions in the
quartz.
0361-0128/98/000/000-00 $6.00
depth: 452 m
49-61.4/7
depth: 94 m
Completely replaced andesite by secondary biotite (potassic alteration). Biotite separates were used for the oxygen and
hydrogen analyses because no quartz or feldspar could be
separated for the oxygen isotope analyses.
37-49/12
depth: 275 m
Completely replaced andesite. Secondary biotite was separated for one run of analyses and whole-rock samples were
used for another run, without any significant difference for
the hydrogen and oxygen results.
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ULRICH ET AL.
depth: 46 m
Feldspar destructively altered andesite with a late quartzpyrite veinlet. The quartz of this vein was used for the oxygen
analyses and the sericite and clay minerals in the associated
alteration halo were used for the hydrogen analyses.
43-47.1/8
depth: 97 m
Andesite or Los Amarillos Porphyry with a strong feldspardestructive overprint and a small (34 mm wide), barren
quartz vein. Main types of inclusions are vapor-rich and aqueous types.
0361-0128/98/000/000-00 $6.00
depth: 192 m
depth: 195 m
Potassically altered Early P3 Porphyry with a quartz-magnetite vein cut by a late pyrite vein. Polyphase brine and vapor
inclusions are the most abundant type of inclusions that were
analyzed for hydrogen isotopes.
38-49/2
55.5-60/4
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