©2004 by Economic Geology

Vol. 99, pp. 39–72

Henderson Porphyry Molybdenum System, Colorado:

II. Decoupling of Introduction and Deposition of Metals during
Geochemical Evolution of Hydrothermal Fluids
ERIC SEEDORFF†
Center for Mineral Resources, Department of Geosciences, 1040 East Fourth Street, University of Arizona, Tucson, Arizona 85721-0077

AND MARCO T. EINAUDI

Department of Geological and Environmental Sciences, Stanford University, Stanford, California 94305-2115

Abstract
Fluorine-rich hydrothermal mineral assemblages developed at Henderson, Colorado, as 12 rhyolitic stocks
of Oligocene age were emplaced, crystallized, and cooled inside a much larger and slightly older, rhyolitic in-
trusion, forming a Climax-type molybdenum deposit. The stocks are grouped into three intrusive centers, and
the mineral assemblages, including ore minerals, are grouped according to their temperatures of formation as
either high-, moderately high, moderate-, or low-temperature assemblages. The latter three groups are termed
lower temperature assemblages, which are subdivided into two suites on the basis of position: above intrusive
centers and on the flanks of the Seriate center. Integration of the mineralogy, sequence, and spatial positions
of mineral assemblages defines the geochemical evolution of hydrothermal fluids, places qualitative constraints
on mass transfer, and provides insight into the development of the geochemical halos that are used in explo-
ration for porphyry orebodies.
A reconnaissance fluid inclusion study targeted the lower temperature assemblages, and a geologic assess-
ment of results indicates that we were unable to identify fluid inclusions from several assemblages. After pool-
ing meaningful results, the ranges of temperatures of formation for each group of lower temperature assem-
blages are moderately high, 600° to 460°C; moderate, 530° to 310°C; and low, 390° to 200°C, with significant
differences in salinity between the two suites of assemblages. The suite formed above intrusive centers was de-
posited by more saline fluids (salinity commonly 28–65 wt % NaCl ± KCl equiv) than the suite formed on the
flanks of the Seriate center (mostly <29 wt % NaCl + KCl equiv). The lower temperature assemblages de-
scribed here do not overlap in space with higher level propylitic alteration, but fluid inclusions in one sample
of propylitized rock indicate temperatures of 320° to 210°C and salinity <29 wt percent NaCl + KCl equiv.
Phase equilibria suggest that, at comparable temperatures, the suite of assemblages that formed above in-
trusive centers formed at higher fS2, fO2, and aK+/aNa+ and slightly lower aK+/aH+ than the suite of assemblages
that formed on the flanks of the Seriate center. From inception of potassic alteration (~600°C) to termination
of sericitic alteration (~300°C), values of log aK+/aH+ of fluids remained essentially constant (~3), but the aF– ·
aH+ of fluids increased. Fluids were undersaturated with respect to topaz during high-temperature silicic and
intense potassic alteration, but topaz precipitated in both suites of assemblages after further fluid evolution.
Topaz formed in certain less intense potassic, transitional potassic-sodic, and sericitic assemblages as the aF- ·
aH+ of fluids increased with decline in temperature and probably pressure, before the fluid again became un-
dersaturated with respect to topaz. Because fluids associated with sericite-pyrite alteration at Henderson were
unusually saline (mostly 29–36 wt % NaCl equiv), cooling of evolved, magmatic fluids (rather than dilution by
meteoric water) likely drove sericitic alteration by cooling through the K-feldspar-sericite buffer at nearly con-
stant aK+/aH+. Indeed, halite-bearing fluid inclusions persist into intermediate argillic assemblages that precip-
itated sphalerite and F-bearing, Mn-rich garnet.
Fluorine was continuously added to wall rocks by hydrothermal fluids along the entire evolutionary paths of
both suites of assemblages. The alkalis underwent a complex history of mass transfer, with the behavior of
potassium fluctuating between periods of strong leaching and strong addition to the rock. Iron was leached at
high to moderately high temperatures and then fixed in the rock at lower temperatures, first mainly as mag-
netite and then as pyrite and minor pyrrhotite and specular hematite. Molybdenum and tungsten show no ev-
idence of any period of significant leaching or recycling.
Each mineralizing intrusion introduced juvenile magmatic hydrothermal fluids containing metals and other
components, but the deposition of metals and other components was staggered over time and a wide temper-
ature range. The order of deposition was Mo to W to Pb-Zn to Mn. The spatial zoning of metals from proxi-
mal to distal around any intrusive center generally—but not always—corresponds to the temporal sequence
early to late. Moreover, the metals that were deposited relatively late tended to be deposited at about the same
time throughout the system, so that Pb-Zn and Mn introduced with the earliest intrusions were not deposited
until much later, after other intrusions and hydrothermal fluids were introduced. Hence, there was progres-
sively greater decoupling between the times of introduction and deposition of metals in the order Mo to W to
Pb-Zn to Mn, and this time delay lengthened for any given component introduced by an earlier intrusion com-
pared to the same component introduced by a later intrusion. The degree of decoupling of introduction and
† Corresponding author: e-mail, seedorff@geo.arizona.edu

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 40 SEEDORFF AND EINAUDI

deposition of components may reconcile discrepancies between differing interpretations of when the majority
of Cu is deposited in porphyry copper deposits.
Hydrothermal mineral assemblages that formed above intrusive centers at Henderson resemble assemblages
in other Climax-type porphyry molybdenum deposits associated with high-silica rhyolites. In contrast, the suite
of assemblages that formed on the flanks of the Seriate center is similar to alteration-mineralization products
formed in porphyry molybdenum deposits related to alkali syenites and in porphyry tungsten-molybdenum de-
posits associated with rhyolites and granites. Hydrothermal assemblages in granite-related molybdenum de-
posits of the differentiated monzogranite suite and granite-related molybdenum-copper deposits have little in
common with either suite of assemblages at Henderson.

Introduction of lower temperature fluids (mostly 530°–200°C), which in-

GEOCHEMICAL investigations provide insight into the geologic cludes the transitions from potassic to sericitic and from
and geochemical processes that form orebodies and their dis- sericitic to intermediate argillic alteration. The first paper
tal expressions, but space-time relationships of metasomatic (Seedorff and Einaudi, 2004) established the space-time rela-
systems must be resolved in the field and laboratory in ad- tionships of lower temperature mineral assemblages by docu-
vance of meaningful geochemical modeling (Barton et al., menting the sequence and abundance of hydrothermal min-
1991a, b). If geochemical investigations are firmly grounded eral assemblages and compositions of hydrothermal minerals
geologically, the resulting model is of greater predictive value and by identifying the flow paths of progressively evolving flu-
than a purely empirical model because the geochemical in- ids, based on careful study of veinlets, their crosscutting rela-
sights aid interpolation between and extrapolation beyond tionships, and the crosscutting contacts of multiple intrusions.
preexisting empirical data points. Sound geochemical models The purpose of the present paper is to characterize the
commonly generate new questions, catalyzing new rounds of physical and chemical environment of fluid evolution at Hen-
field, analytical, and theoretical investigation. derson, encompassing the introduction and deposition of
Diversity among deposits, as embodied in the variations on metals and other components and the resultant zoning pat-
a theme concept of Gustafson and Hunt (1975), is widely ap- terns. The environment is constrained by coexisting minerals
preciated for porphyry-related deposits. Nonetheless, the and their compositions, characteristics of veins, phase equi-
geochemical evolution of hydrothermal fluids as a function of libria, and results of fluid inclusion study. Pressure and depth
space, time, temperature, and composition is well docu- information arises from geologic constraints, which are tested
mented for few porphyry-related hydrothermal systems (as is against phase equilibria. We deduce the evolution of hy-
apparent from Gustafson, 1978; Einaudi, 1982; Clark, 1993; drothermal fluids and the role of topaz by integrating field re-
Lang et al., 1995), because comprehensive, detailed, field- lationships with the geochemical environments of assem-
based studies, which are themselves uncommon, must be co- blages. We illustrate fluid evolution by geochemical paths in
ordinated with subsequent geochemical and petrologic inves- phase diagrams, which reveal sources of diversity of hy-
tigations to deduce geochemical paths. Although a few drothermal mineral assemblages. The mineralogy, sequence,
igneous-related hydrothermal systems have been successfully and distribution of assemblages provide qualitative con-
modeled (e.g., Heinrich and Ryan, 1992), the documentation straints on mass transfer. The spatially extensive time lines
of geochemical evolutionary paths has progressed only mod- available at Henderson (Seedorff and Einaudi, 2004) permit
estly since the definition of a main line ore-forming environ- us to evaluate (1) the sources of chemical components, (2) the
ment by Barton (1970); consequently, the causes of zonation degree of recycling of ore components, and (3) the relative
within a deposit and sources of diversity between deposits are importance of changes over time in compositions of juvenile
incompletely understood. Although some causes of zonation magmatic hydrothermal fluids that were injected into the hy-
and sources of diversity have been confirmed and others are drothermal system versus temporal evolution of migrating hy-
predicted by experimental data and theoretical models (Meyer drothermal fluids. Synthesis of the data constrains the origin
and Hemley, 1967; Barnes, 1975; Gustafson, 1978; Hemley et of sericitic and intermediate argillic fluids at Henderson and
al., 1980; Barton et al., 1991a; Candela, 1992; Hemley and provides a context for comparing alteration-mineralization
Hunt, 1992; Cline, 1995; Dilles et al., 2000a), significant oper- products in porphyry deposits.
ative processes may remain unidentified. Moreover, variable This study builds on previous contributions to the under-
geochemical paths within single hydrothermal systems (e.g., standing of alteration-mineralization at Henderson (MacKen-
Einaudi, 1977) have rarely been recognized and sources of zie, 1970; White and MacKenzie, 1973; Ranta et al., 1976;
such variability have hardly been examined. Wallace et al., 1978; Gunow et al., 1980; White et al., 1981;
The Henderson porphyry molybdenum deposit is ideally Carten et al., 1988a, b), especially on the work of MacKenzie,
suited to a study of wall-rock alteration and metal deposition White, and Carten. The fluid inclusion portion builds on ear-
because it has been studied over a protracted period of time lier work by Kamilli (1978) and White et al. (1981) and com-
(Meyer and Hemley, 1967, p. 166–167); indeed, it stands as plements past and ongoing studies directed at the high-tem-
one of the best-documented porphyry deposits in the world. perature mineral assemblages (Carten, 1987; Carten et al.,
Wallace et al. (1978), White et al. (1981), and Geraghty et al. 1988c).
(1988) established the geologic setting, and Carten et al.
(1988a, b) described the development of silicic and intense Geologic Setting and Intrusive History
potassic alteration at high temperatures (generally above 500°C). Henderson and Urad constitute a stacked pair of Climax-
This paper is part of a study examining the evolutionary paths type porphyry molybdenum orebodies associated with Oligocene

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by Edilber A. Chipana
 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 41

intrusions of biotite high-silica rhyolite at Red Mountain, Methods

Clear Creek County, Colorado (Wallace et al., 1978; White et In this paper, compositions of topaz and sericite-muscovite
al., 1981; Geraghty et al., 1988; Carten et al., 1993; Wallace, are used in conjunction with geologic reconstructions, cross-
1995). The older, shallower, and much smaller Urad deposit cutting relationships, phase equilibria, and fluid inclusion re-
(Fig. 1) is hosted by stocks of rhyolite porphyry and by the sults to constrain the evolving geochemical environment in
Silver Plume Granite, a Proterozoic biotite-muscovite gran- terms of temperature, pressure, relative activity ratios and
ite. The Urad orebody is cut off by a cylindrical intrusion, the products, and sulfur and oxygen fugacity. Treatment of halo-
Red Mountain porphyry, which flares out into a larger body, gen fugacities (e.g., Munoz, 1984; van Middelaar and Keith,
the Urad porphyry, at depth (Wallace et al., 1978). 1990) is beyond the scope of this contribution and is deferred
The Henderson deposit is associated with a dozen or more, to a subsequent communication. All phase diagrams were
small, texturally and compositionally zoned stocks (Carten et constructed using SUPCRT, an internally consistent thermo-
al., 1988a, b) that intruded the Urad porphyry (Fig. 1). The dynamic database (Helgeson et al., 1978). Thermodynamic
stocks are grouped into three closely spaced intrusive centers, data for fluor-topaz, however, were derived from the data of
Henderson, Seriate, and Vasquez. The Henderson orebody Barton et al. (1982) after adjustment for consistency with the
consists of three overlapping ore zones, each of which is asso- SUPCRT database (Seedorff, 1987, app. E). The model ther-
ciated with one of the intrusive centers. The three ore zones modynamic data for hydroxyl-topaz (Barton, 1982) were sim-
are themselves composite, because each individual stock de- ilarly adjusted, and the proton-avoidance model of Barton
veloped its own ore shell. The Henderson intrusive center is (1982) was adopted for topaz solid solutions. The fluid inclu-
composed of five stocks, several prominent dikes, and a brec- sion methodology is described in the Appendix.
cia body. The focus of intrusion subsequently shifted to the
east-northeast, where the four stocks of the Seriate center in-
truded, and finally shifted to deeper levels, where three stocks Summary of Hydrothermal Mineral Assemblages
of the Vasquez center were emplaced (for further information, Assemblages herein are grouped by their temperatures of
see Carten et al., 1988b; Seedorff and Einaudi, 2004). formation: high, moderately high, moderate, and low based
on geologic relationships and mineralogy prior to study of as-
sociated fluid inclusions. In the text, each complete assem-
WEST EAST blage is represented by an abbreviation in capital letters (Fig.
52N-N63E-58N Cross Section 2). The reader is referred to the companion paper (Seedorff
Red Mountain Elev. and Einaudi, 2004) regarding the nomenclature and use of
Ft notation in citing mineral assemblages.
12,000
Carten et al. (1988a, b) studied high-temperature alter-
URAD
ation-mineralization, which can be treated in terms of two
OREBODY simplified mineral assemblages that are related to veins filled
with quartz + fluorite ± molybdenite: a silicic type, quartz +
Pre-Red fluorite ± (molybdenite), denoted by QTZ-FL, and an intense
Mountain
stocks Red Mountain potassic type, K-feldspar + fluorite ± quartz ± molybdenite ±
(biotite), denoted by QTZ-KSP-MO (Fig. 2).
Lower temperature assemblages, which are the subject of
Precambrian this study, include all but the high-temperature assemblages.
10,000
Silver Plume The lower temperature assemblages are subdivided into two
Granite
suites on the basis of their spatial positions: most abundant
above intrusive centers, and restricted to the flanks of the Se-
Urad fine riate center (Figs. 2–3).
The suite of assemblages above intrusive centers includes
HENDERSON OREBODY
Urad normal the moderately high temperature assemblages MOTTLED
KSP-QTZ and MT-KSP, the moderate-temperature assem-
blages TPZ-PY and SER-PY, and the low-temperature assem-
blages PY-CLAY, SPHAL, GAR, and RHOD (Figs. 2–3). As a
H 8,000
group, this suite of assemblages is distinguished by the pres-
S ence of K-rich hydrothermal alkali feldspar in moderately
high temperature assemblages, magnetite deposited with K-
V feldspar but not with sericite, topaz occurring almost entirely
Post-Urad
stocks 0 METERS 500
in a single, pyritic, feldspar-destructive assemblage, and a va-
480H
riety of pyrite-bearing assemblages formed at low tempera-
50E BEND 60E BEND 70E tures, in greatest abundance at high levels in the system.
The suite of assemblages on flanks of the Seriate center
FIG. 1. Cross section of Red Mountain, showing Urad and Henderson contains the moderately high temperature assemblages BIO-
orebodies and Henderson (H), Seriate (S), and Vasquez (V) intrusive centers
related to the Henderson orebody. Tick marks at top and bottom and labels
KSP and TPZ-BIO-MT, the moderate-temperature assem-
at bottom show bends in section, mine coordinates, and location of the 480 blages TPZ-MT, SER-MT, and GREEN BIO, and only one
H cross section that has been featured in many publications on Henderson. low-temperature assemblage, PO, because the two suites of

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 Suite of Assemblages Developed Above Intrusive Centers Suite of Assemblages Developed On The Flanks of the Seriate Center
42
Lower Temperature Asemblages Above Intrusive Centers Lower Temperature Asemblages on Flanks of Seriate

by Edilber A. Chipana
Moderately Moderately
Group of High High Moderate Group of High High Moderate Low
Assemblages Temperature Temperature Temperature Low Temperature Assemblages Temperature Temperature Temperature Temp.

Mineral Mineral

Mineral
Assemblage
(ABBREVI-
ATION)
QTZ-FL
QTZ-KSP-MO
MOTTLED
KSP-QTZ
MT-KSP
TPZ-PY
SER-PY
PY-CLAY
SPHAL
GAR
RHOD
Mineral
Assemblage
(ABBREVI-
ATION)
QTZ-FL
QTZ-KSP-MO
BIO-KSP
TPZ-BIO-MT
TPZ-MT
SER-MT
GREEN BIO
PO

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Quartz Quartz ?
Fluorite Fluorite ?
Molybdenite Molybdenite
K-feldspar K-feldspar
K-Na-feldspar K-Na-feldspar
Na-feldspar Na-feldspar
Magnetite Magnetite
Hematite Hemmatite
Pyrite Pyrite
Pyrrhotite Pyrrhotite
Ilmenorutile Ilmenorutile
Rutile Rutile
Leucoxene Leucoxene
Topaz Topaz
Wolframite Wolframite
Brown biotite Brown biotite
Green biotite Green biotite ?
Muscovite Muscovite

42

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Sericite Sericite ?
Clay Clay ?
Garnet Garnet
Sphalerite Sphalerite
Galena Galena
SEEDORFF AND EINAUDI

Chalcopyrite Chalcopyrite
Barite Barite
Rhodochrosite ? Rhodochrosite

Key Mineral presence in the assemblage

Always
Commonly, but not always
Uncommonly
Not always and, where present, only in minor amounts
Rarely
? Uncertain assignment to assemblage

FIG. 2. Graphic definition of hydrothermal mineral assemblages in the Henderson deposit, separated by suites of lower temperature assemblages (inspired by fig. 5
of Gustafson and Quiroga G., 1995). The high-temperature assemblages (simplified from Gunow, 1983; Carten et al., 1988b) are shown next to each suite and also lo-
cally include zircon, monazite, and apatite (omitted). Assemblages are arranged across the top of the figure and minerals along the left side. Abbreviations for assem-
blages are based on the following mineral abbreviations: BIO = biotite, GAR = garnet; GREEN BIO = green biotite, KSP = K-feldspar, MT = magnetite, PO =
pyrrhotite, PY = pyrite, QTZ = quartz, RHOD = rhodochrosite, SER = sericite, SPHAL = sphalerite, and TPZ = topaz. This is not a paragenetic diagram applicable to
the entire deposit because of the cyclicity of the Henderson system, the differences between cycles in different intrusive centers, and the merging of suites at low tem-
peratures (see Seedorff and Einaudi, 2004). Nonetheless, progression from high to low temperatures in each suite generally represents an evolutionary path for fluids
that formed each suite of assemblages.
 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 43

HIGH-TEMPERATURE ASSEMBLAGES
QTZ-FL
> 50 vol % Feldspars → Quartz
WEST EAST
52N-N63E-58N Section (silicic alteration)
10,000
in
QTZ-KSP-MO
a
nt mo
ou
M mt Top of visible molybdenite
R ed
mo
> 5 vol % Quartz ± Fluorite ± Molybdenite
mottled veins (guide intense potassic alteration)

MODERATELY HIGH-TEMPERATURE
B-
M ASSEMBLAGES
T-

S B-K MOTTLED KSP-QTZ BIO-KSP

H Absent Absent
mt B-K
mottled
Trace - 40 vol %
mt V cut off Present
7,000 Absent
0 meters 500
480H MT-KSP TPZ-BIO-MT
50E BEND 60E BEND 70E A Absent Absent
mt Rare - 10
>10 vol % T-B-M
vol % mostly trace - 10 vol %
mt Absent Absent
Absent cut off

MODERATE-TEMPERATURE
WEST EAST ASSEMBLAGES
52N-N63E-58N Section TPZ-PY TPZ-MT GREEN-BIO
10,000 Trace - 5 vol %
> 10
GAR vol %
PY in
R- nta
Absent
SE ou > 3 vol %
M
d SER-PY SER-MT
Re
Absent > 10 Absent
Trace - 5 vol %
Trace - 10 vol %
vol % Absent cut off Absent
> 5 vol %

S LOW -TEMPERATURE ASSEMBLAGES

SE
H R-
PY
PO SPHAL RHOD
Sparse Sparse
Mostly
7,000 trace - Common-abundant
0 500 V 3 vol % occurrences Abundant-common
meters Absent
480H Sparse occurrences
GAR
50E BEND 60E BEND 70E B Abundant Sparse

FIG. 3. Simplified, time-integrated view of alteration-mineralization at Henderson, showing simplified distribution and
abundances of hydrothermal mineral assemblages. A. High- and moderately high temperature assemblages. B. Moderate-
and low-temperature assemblages. See Figure 2 for definitions and abbreviations of assemblages.

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by Edilber A. Chipana
 44 SEEDORFF AND EINAUDI

assemblages merge at low temperatures (Figs. 2–3). The suite temperatures (Figs. 2–3; see also Seedorff and Einaudi, 2004,
of six assemblages that formed on the flanks of the Seriate table 6). An order-of-magnitude estimate of the Mn content
center is distinguished by widespread and locally abundant corresponding to the outline of the Mn zone of Figure 4D is
hydrothermal biotite, widespread topaz, appearance of alkali 2,000 ppm.
feldspars of K-rich, K-Na, and Na-rich compositions, the The overall metal zonation of Henderson (Fig. 4A-D), thus,
abundance of magnetite, and local pyrrhotite. is highly complex.
Distribution of Metals Temperature and Salinity Estimates—
The only metal of economic importance at Henderson is Fluid Inclusion Study
Mo, but elements such as W, Pb, Zn, Cu, Bi, Ag, and Mn are
geochemically anomalous and are of exploration interest be- Purpose and strategy
cause they are more widely dispersed than Mo (Bright, 1974; A reconnaissance fluid inclusion study was conducted pri-
Westra and Keith, 1981). marily to assign approximate temperatures of formation to
At Henderson, practically every core interval has been an- the mineral assemblages for incorporation into a model of the
alyzed for Mo (reported at Henderson in terms of MoS2). The geochemical evolution of the hydrothermal system. Because
distribution of Mo and its relationship to individual stocks are porphyry systems are characterized by a multiplicity of cross-
shown in Figure 4A (Carten et al., 1988b, figs. 3–4, 13–15; cutting, partially superimposed events (e.g., Gustafson, 1978;
Seedorff and Einaudi, 2004, figs. 2–3, for greater information Titley, 1982), samples containing a minimum number of geo-
and detail). Note that the Mo pattern mimics the distribution logic events were sought for fluid inclusion investigation (see
and abundance of the high-temperature assemblage QTZ- App.). The strategy (Seedorff, 1987) is to determine the fluid
KSP-MO (Fig. 3; see also fig. 5 of Seedorff and Einaudi, characteristics of each assemblage based on relatively few mi-
2004) because this assemblage contains most of the Mo (as crothermometric measurements from a modest number of
molybdenite) in the Henderson deposit (Fig. 2). samples. An ideal sample would contain one assemblage (the
Although nine, long holes drilled during exploration of the target assemblage), would not contain crosscutting or super-
deposit were analyzed for a large suite of elements (Bright, imposed events, and would occur in a region of the deposit
1974), elements such as W, Zn, Cu, and Mn have not been where other assemblages are absent. Interpretations are
routinely assayed. Nonetheless, the distribution of many met- based on interpolation and extrapolation of data in space and
als can be estimated (Fig. 4) because we logged both the oc- time based on the best-known geologic parameters, princi-
currence and relative abundance of metal-bearing minerals in pally the distribution and abundance of assemblages and their
the various assemblages (Fig. 2) and the distribution and relative ages.
abundance of assemblages (Fig. 3). Many samples selected from Henderson contain abundant
Tungsten rarely exceeds 100 ppm WO3 and thus is far less evidence of multiple events, in spite of every attempt to
abundant at Henderson than at Climax (Wallace et al., 1978, choose samples that are geologically simple to interpret. Al-
p. 361, 364). Wolframite (~77 wt % WO3), the principal con- though some fluid inclusions in vein-filling minerals are of ob-
tributor of W at Henderson, is nonetheless commonly visi- vious secondary origin, most are of ambiguous origin; similar
ble with a hand lens, mostly in the moderate-temperature difficulties have been acknowledged reluctantly by other stu-
assemblage TPZ-PY (Figs. 3, 4B; see also Seedorff and Ein- dents of fluid inclusions in porphyry systems (e.g., Nash and
audi, 2004). Ilmenorutile, containing ~1 wt percent WO3, is Theodore, 1971, p. 389, 398; Eastoe, 1978, p. 725; Bodnar
another W-bearing hydrothermal mineral present at Hen- and Beane, 1980, p. 882; White et al., 1981, p. 299; Roedder,
derson (Gunow, 1983). It occurs in many assemblages in 1984, p. 446–447; Theodore et al., 1992, p. 255–256, 269,
trace abundance (Fig. 2), including several from the suite on 275; Muntean and Einaudi, 2001, p. 767). In some deposits,
the flanks of the Seriate center. To illustrate the point that samples with more favorable characteristics have been found,
zones of concentration of certain mineral assemblages can and workers have concentrated their studies on these (e.g.,
be used to define metal distribution, Figure 5 shows the oc- Roedder, 1971; Wilson et al., 1980, p. 47–48; Cline and Bod-
currences of wolframite logged on two cross sections com- nar, 1994, p. 1781–1782). In the case of many mineral assem-
pared to the distribution and abundance of the assemblage blages, samples with such characteristics have not been found
TPZ-PY. at Henderson.
The low-temperature assemblages SPHAL and GAR con- Suitable fluid inclusions were studied in vein-filling miner-
tain most of the Zn as sphalerite and Pb as galena (Fig. 4C); als, in hydrothermal minerals in a few wall-rock alteration
an order-of-magnitude estimate of the metal contents corre- envelopes, and in quartz phenocrysts that are cut by a vein-
sponding to the outline of the Pb-Zn zone of Figure 4C is 500 let or that are in their alteration envelope. Standard petro-
ppm each of Pb and Zn. The trace occurrence of Cu at Hen- graphic observations were recorded, and heating runs were
derson is virtually restricted to microscopic inclusions of chal- performed. Few freezing runs were attempted, because
copyrite in sphalerite (Seedorff, 1988); thus, the distribution salinities could be obtained from the halite-bearing samples
of Cu should follow Zn. Trace element dispersion patterns from heating runs, and the halite-absent inclusions generally
(Bright, 1974) suggest that the distribution of the SPHAL as- were too small, given the optical quality of the samples (Fig.
semblage should also outline the distribution of Bi and Ag. 6), to see melting phenomena. The Appendix contains infor-
The low-temperature assemblages GAR and RHOD are mation on the classification and characteristics of fluid inclu-
the most important hosts of Mn, although minor Mn was sions and use of ideal geochemical systems to model their
fixed in micas in various assemblages formed at higher compositions.

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 45

52N-N63E-58N Section 52N-N63E-58N Section

Elev., Ft Molybdenum Elev., Ft Tungsten
10,000 10,000
n Wt % MoS 2 n
ai ai Absent
nt > 0.7 nt
ou 0.5 - 0.7 ou Common Trace
M M
R ed 0.2 - 0.5
Re
d Trace
0.1 - 0.2 Absent
< 0.1

W
W

Mo S
Mo H
S
H
7,000 V 7,000
V
0 meters 500 Mo 0 meters 500
480H 480H
50E BEND 60E BEND 70E
A 50E BEND 60E BEND 70E B

52N-N63E-58N Section 52N-N63E-58N Section

Elev., Ft Elev., Ft
in

10,000 10,000
nta

ou Pb-Zn Lead-Zinc Manganese

M in
nta
d Sparse Mn Rhodochrosite
Re ou Sparse
Common-abundant M
d
occurrences
Re Common

Sparse Abundant
Pb-Zn
Mn Common
H H
S Sparse
S Garnet

Mn Abundant
Pb-Zn
7,000 7,000
0 meters 500 V 0 meters 500 V
480H 480H
50E BEND 60E BEND 70E C 50E BEND 60E BEND 70E D

FIG. 4. Simplified, time-integrated view of metal distribution at Henderson, showing zones of Mo, W, Pb-Zn, and Mn en-
richment on section 52N-N63E-58N. H, S, and V denote the Henderson, Seriate, and Vasquez centers, respectively. A.
Quantitative distribution of Mo, which is present predominantly in the high-temperature assemblage QTZ-KSP-MO, based
on assayed drill holes. For visual reference, black circles are placed in the center of the Mo ore zone related to each of the
three intrusive centers, although the ore zones are themselves composite features, created by overlap of ore shells formed
about each mineralizing stock. A thin arrow from an open circle enclosing Mo points to each of the filled black circles. The
sizes of the black circles are scaled roughly to the Mo content of each ore zone. Around each black dot, there are open white
arrows representing the principal directions that ore fluids initially were directed, based on orientations and relative abun-
dances of veins. B. Qualitative distribution of W, present predominantly in the moderate-temperature assemblage TPZ-PY,
based on the distribution and abundance of TPZ-PY logged in drill core. Open pentagons enclosing W are placed at the ap-
proximate centers of the two, overlapping tungsten zones, one over the Henderson center and the other over the Seriate cen-
ter. C. Qualitative distribution of Pb-Zn, present predominantly in the low-temperature assemblage SPHAL, based on dis-
tribution and abundance of SPHAL logged in drill core. Open rectangles enclosing Pb-Zn are placed at the approximate
centers of the three Pb-Zn zones, one over each of the three intrusive centers. D. Qualitative distribution of Mn, present
predominantly in the low-temperature assemblages GAR and RHOD, based on distribution and abundance of GAR and
RHOD logged in drill core. Open triangles enclosing Mn are placed at the approximate centers of the three Mn zones, one
over each of the three intrusive centers.

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 46 SEEDORFF AND EINAUDI

WEST 52N-N63E-58N Section EAST NORTHWEST 480 H Section SOUTHEAST

Elev., Ft WOLFRAMITE Elev., Ft WOLFRAMITE
10,000 OCCURRENCES LOGGED 10,000 OCCURRENCES LOGGED
IN DRILL HOLES IN DRILL HOLES

Drill hole trace ain Drill hole trace

ount
in Red M
nta Wolframite in TPZ-PY Wolframite in TPZ-PY
ou
dM Wolframite in SER-PY
Re

DISTRIBUTION DISTRIBUTION
OF TPZ-PY OF TPZ-PY
ASSEMBLAGE ASSEMBLAGE
> 3 vol % > 3 vol %
0.1 - 3 vol % 0.1 - 3 vol %
Trace Trace
7,000 Absent
7,000 Absent
0 METERS 500 0 METERS 500
480H N63E
50E BEND 60E BEND 70E A 50E B 60E 70E

FIG. 5. Wolframite occurrences logged on section 52N-N63E-58N and section 480 H, compared to limits and isopleths
of abundance of the moderate-temperature assemblage TPZ-PY.

15µm A B

BIO-KSP

15µm

SER-PY

FIG. 6. Photographs of fluid inclusions taken at 25ºC prior to heating. A. Typical fluid inclusion distributions, illustrating
abundance of small fluid inclusions. The target assemblage for this sample (H-499-295.2) is BIO-KSP. The fluid inclusions
are hosted by vein-filling quartz, and the large fluid inclusion (arrow) has liquid, a vapor bubble, and daughter minerals of
halite and hematite(?); upon heating, halite melted at 108.1ºC and liquid and vapor homogenized at 480.5ºC. B. Abundant
halite-bearing fluid inclusions typical of the SER-PY assemblage. Fluid inclusions in this sample (CX-158-1416) are hosted
by a quartz phenocryst that is cut by a sericitic veinlet. Fluid inclusions from the SER-PY assemblage commonly have liquid,
a vapor bubble, daughter minerals of halite and hematite (arrow), and one or more unidentified phases.

Results and interpretation from different samples so that the data gathered from sam-
ples containing only the youngest events can be used to strip
Results of microthermometric measurements are pre- off effects of younger events (i.e., secondary inclusions) su-
sented in Figures 7 and 8. An unconventional approach, sim- perimposed on older events. A review of the results and in-
ilar to that of Preece and Beane (1982, fig. 16, p. 1634) and terpretations (summarized in Table 1) follows, proceeding
Shaver (1984a, b) but unlike that of most fluid inclusion stud- from lower to higher temperatures.
ies, is adopted to interpret the results. The approach involves Samples in which the low-temperature group of assem-
a geologic deduction of which fluid inclusions in a sample, if blages was targeted exhibit a surprisingly large proportion of
any, might be representative of the fluids from which a par- halite-bearing fluid inclusions (salinities as high as 37 wt %
ticular assemblage formed. Deduction follows from (1) mea- NaCl equiv). Fluids with temperature-salinity characteristics
surements made on individual samples (Fig. 7, left side, and similar to those of the low-temperature assemblages appear
Fig. 8); (2) geologic relationships regarding the distribution to be represented in the data gathered from samples in which
and relative age of formation of assemblages (documented in other, earlier assemblages were targeted (Figs. 7–8).
Seedorff and Einaudi, 2004), which are used to help identify Among the moderate-temperature assemblages, fluid in-
possible sources of secondary inclusions in a given sample clusions attributed to the SER-PY assemblage (in veins with-
(right side of Fig. 7); and (3) comparison of data obtained out inner envelopes of TPZ-PY) exhibit similar salinities but

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 47

TABLE 1. Reconnaissance Fluid Inclusion Study of Lower Temperature Assemblages

Group Assemblage1 Temperature2 Salinity3

Moderately high temperature

MOTTLED KSP-QTZ No data4 No data4
MT-KSP 460–530 <29
BIO-KSP* 500–600? Mostly <29?
TPZ-BIO-MT* No data4 No data4
Moderate temperature
TPZ-PY (with an outer envelope of SER-PY) 400–500 Mostly 30–65
TPZ-PY (with an outer envelope of GREEN BIO) 410–510 <29
SER-PY (beyond an inner envelope of TPZ-PY) 400–500 Mostly 30–65
SER-PY (without an inner envelope of TPZ-PY) 310–470 Mostly 29–36
TPZ-MT* (without an outer envelope of SER-MT) No data No data
TPZ-MT* (with an outer envelope of SER-MT) 400–530 <29
SER-MT* (beyond an inner envelope of TPZ-MT) 400–530 <29
SER-MT* (without an inner envelope of TPZ-MT) No data No data
GREEN BIO* (beyond an inner envelope of TPZ-PY) 410–510 <29
GREEN BIO* (without an inner envelope of TPZ-PY) No data No data
Low temperature
PO* No data No data
PY-CLAY5 200–350 Mostly <29–35
SPHAL (without an outer envelope of GAR) 210–370, mostly 280–330 Mostly 28–37
SPHAL (with an outer envelope of GAR) 200–380, mostly 200–300 Mostly 28–36
GAR (beyond an outer envelope of SPHAL) 200–380, mostly 200–300 Mostly 28–36
RHOD 200–390 <29
Propylitic 210–320 <29

1 See Figure 2 and Seedorff and Einaudi (2004, table 1) for definitions and abbreviations of assemblages (except propylitic—see text).; an asterisk (*) de-

notes a member of the suite of assemblages on the flanks of the Seriate center; the remaining assemblages are members of the suite of assemblages above in-
trusive centers; for this compilation, compositions of fluids are assumed to have been similar from the vein filling to the edge of an alteration envelope so that
microthermometric data are applied to all assemblages in a zoned envelope, regardless of the position of the fluid inclusions that were measured
2
Interpreted range of homogenization temperatures (°C)
3
Interpreted range of salinities, in wt percent NaCl equiv and wt percent NaCl + KCl (see App.)
4
None of the fluid inclusions measured in the sample targeted for this assemblage is thought to be related to this assemblage
5
Not a targeted assemblage in any sample, but secondary inclusions in some samples are interpreted to be related to this assemblage

higher homogenization temperatures than low-temperature low-temperature fluid inclusions in samples from this region
assemblages such as SPHAL and GAR (Figs. 7–8). Moreover, of the deposit similarly lack such daughters (Fig. 7).
the temperatures (310°–470°C) and salinities (generally Data from samples in which moderately high temperature
29–36 wt % NaCl equiv or roughly 6–10 m NaCl solutions; all assemblages were targeted are difficult to interpret, although
fluid inclusions homogenized by vapor disappearance) of the it is apparent that most fluid inclusions studied probably are
SER-PY assemblage are considerably higher than the values secondary fluid inclusions related to assemblages formed at
reported for sericitic alteration in most porphyry deposits lower temperatures. For the BIO-KSP assemblage, some fluid
(e.g., 250°–350°C, <20 wt % NaCl equiv; Beane and Titley, inclusions probably are secondary fluid inclusions that were
1981, p. 253–254; Hedenquist et al., 1998, p. 385). Where the contributed by fluids associated with high-temperature assem-
SER-PY assemblage fringes an inner envelope of the TPZ-PY blages (QTZ-FL and QTZ-KSP-MO) of a younger intrusive
assemblage (Figs. 7–8), the inferred temperatures are even hydrothermal cycle associated with the underlying Vasquez
higher, approaching 500°C, and salinities locally exceed 50 wt stock. Although none was present in the samples studied,
percent NaCl + KCl equiv (sylvite may be present at room high-temperature veins related to the Vasquez center are pre-
temperature and some inclusions homogenize by halite disso- sent in the regions from which all of the BIO-KSP assemblage
lution). Neither daughter salt is present in fluid inclusions samples were collected (Figs. 3, 7). For the sample in which
from the TPZ-PY assemblage in vein types where envelopes the MOTTLED KSP-QTZ assemblage is the targeted assem-
of the GREEN BIO assemblage fringe the TPZ-PY assem- blage (and for four other histograms of Fig. 7), none of the
blage, although the homogenization temperatures are compa- fluid inclusions is thought to be representative of the fluids
rable (Fig. 7; Table 1). Moderate-temperature assemblages from which the assemblage(s) formed. If one were to assume
that are members of the suite on the flanks of the Seriate cen- that the fluid inclusions measured for the MOTTLED KSP-
ter (TPZ-MT, SER-MT, GREEN BIO) appear to be associ- QTZ assemblage are representative of the fluids from which
ated with fluid inclusions that lack daughter salts. Most of the the assemblage formed, then the earlier, K-feldspar-bearing

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 48 SEEDORFF AND EINAUDI

MOTTLED KSP-QTZ
TPZ-BIO-MT *
GREEN BIO *

QTZ-KSP-MO
Sample (number of measurements)

BIO-KSP *
SER-MT *
TPZ-MT *
PY-CLAY
Propylitic
HOMOGENIZATION TEMPERATURE (°C) Target Assemblage(s)

MT-KSP
SER-PY

QTZ-FL
TPZ-PY
SPHAL
RHOD
Host and Site

GAR

PO *
200 250 300 350 400 450 500 550 600 650
4 H - 321 - 314 (n = 25) S
MOTTLED KSP - QTZ 10
2 50
Recrystallized quartz
0 L
S
H - 268 - 380 (n = 8) 10
2 MT - KSP 50
0 Vein - filling quartz L
4 S
H - 499 - 295.2 (n = 28) 10
2 BIO - KSP 50
0 Vein - filling quartz L
8
6
4 H - 488 - 713.9 (n = 45) S
2 BIO - KSP 10
Vein - filling quartz 50
0 L
4 S
H - 430 - 452.5 (n = 11) 10
2 BIO - KSP 50
0 Vein - filling quartz L
4 S
H - 074 - 24 (n = 13) 10
2 TPZ - PY, SER - PY 50
0 Vein - filling quartz L
4 H - 074 - 24 (n = 13) S
TPZ - PY, SER - PY 10
2 50
Quartz in SER - PY
0 envelope L
10
FREQUENCY

8
6
4 CX - 158 - 1416 (n = 50) S
SER - PY 10
2 Quartz phenocryst cut by 50
0 veinlets L
4 CX - 98 - 2908 (n = 21) S
TPZ - MT, SER - MT 10
2 Quartz phenocryst in 50
0 TPZ - MT envelope L
S
H - 323 - 842 (n = 2) 10
2 TPZ - PY, GREEN BIO 50
0 Topaz in TPZ - PY envelope L
H - 323 - 842 (n = 6) S
TPZ - PY, GREEN BIO 10
2 Quartz phenocryst in 50
0 GREEN BIO envelope L
S
H - 471 - 255 (n = 10) *
2 TPZ - PY, GREEN BIO *
0 Vein - filling topaz L
4 H - 471 - 255 (n = 17) S
TPZ - PY, GREEN BIO *
2 Quartz phenocryst in *
0 GREEN BIO envelope L
4 CX - 93 - 814 (n = 17) S
SPHAL 10
2 50
Quartz phenocryst cut
0 by veinlet L
4 CX - 91 - 1059 (n = 13) S
GAR 10
2 50
Quartz phenocryst in GAR
0 envelope L
4 CX - 163 - 499 (n = 19) S
RHOD 10
2 50
Quartz phenocryst in GAR
0 envelope L
S
CX - 158 - 445 (n = 5) 10
2 Propylitic 50
0 Vein - filling quartz in epidote L
200 250 300 350 400 450 500 550 600 650 + pyrite + quartz veinlet
Inclusion containing halite daughter Inclusion containing halite and sylvite Vapor - rich inclusion that
mineral that homogenizes by daughter minerals that homogenizes by homogenizes by V + L → V
L + hal + V → L + V → L L + hal + syl + V → L + hal + syl → L + hal → L
Inclusion containing halite daughter Inclusion containing rhombohedral Liquid - rich inclusion that
mineral that homogenizes by daughter mineral that homogenizes homogenizes by critical behavior
L + hal + V → L + hal → L by L + R + V → L + V → L
Inclusion containing halite and sylvite Liquid - rich inclusion that Obviously secondary inclusion
daughter minerals that homogenizes by homogenizes by L + V → L (used with other symbols)
L + hal + syl + V → L + hal+ V → L + V → V
Note: Daughter minerals other than those mentioned may be present in any type of inclusion.

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 49

assemblage of MOTTLED KSP-QTZ would have formed at Third, none of the 300 fluid inclusions (including those
temperatures <370°C, which is substantially below that of the hosted by quartz phenocrysts) of this study homogenized at
later, feldspar-destructive assemblages TPZ-PY (400°–500°C) temperatures below 200°C (Fig. 7). In addition, the his-
and SER-PY (310°–440°C). This latter alternative is rejected togram of White et al. (1981, fig. 30) shows roughly 200 ho-
because it is geologically less probable. The argument for the mogenization temperatures, with none below 225°C. Either
former, preferred alternative is strengthened by the number fluids cooler than 200°C were present but were not trapped
of low-temperature assemblages (inferred to be responsible as fluid inclusions or cooler fluids may not have circulated
for the fluid inclusions that were measured; Fig. 7) that were through the mineralized core of the hydrothermal system
superimposed on the same general region where the MOT- (Seedorff and Einaudi, 2004). Homogenization temperatures
TLED KSP-QTZ assemblage was developed, near the apices of fluid inclusions from base and precious metal veins at the
of intrusions (Fig. 3). The spatial distribution of the assem- periphery of the district (Corbetta, 1986) do include some
blage and its texture also point to the possibility that fluids values below 200°C, although most are between 200° and
boiled during its formation (Seedorff and Einaudi, 2004). 300°C—roughly comparable to values observed at Hender-
Three additional interpretations are drawn from the results son from a sample that exhibits propylitic alteration (Fig. 7).
(Table 1). First, there appears to be a difference in the salin-
ities of fluids that formed the two suites of assemblages. Depth Constraints and Pressure Estimates
High-salinity (i.e., halite saturated at room temperature) flu- Early geologic reconstructions made by Ogden Tweto were
ids commonly are associated with the suite of assemblages used to place the top and base of the Henderson orebody at
that formed above intrusive centers (Figs. 2–3, 7–8). Liquid- depths of 1.7 and 2.3 km, respectively (Wallace, 1974; White
rich fluid inclusions without halite or sylvite daughter miner- et al., 1981, p. 287), below a paleosurface that is likely to have
als (Fig. 7) appear to characterize the suite of assemblages on been a rhyolite dome field with associated ash-flow tuffs (e.g.,
the flanks of the Seriate center. These compositional differ- Keith et al., 1986; Stein and Crock, 1990). In light of the ef-
ences may be inherited from higher temperatures, because fects of subsequently identified postore faulting and tilting in
Carten (1987) has identified two types of high-temperature the region, these paleodepths have been revised by Geraghty
fluids that have different spatial distributions—one a Cl-rich et al. (1988) to 2.8 km for the top of the Henderson and Seri-
fluid, the other a low-Cl, F-rich, Fe- and K-bearing alumi- ate centers and 3.1 km for the top of the Vasquez center. Con-
nosilicate fluid. Lower temperature fluids on the flanks of the sidering the types of igneous and hydrothermal textures ob-
Seriate center may represent evolved versions of the low Cl, served in the deposit (Wallace et al., 1978; White et al., 1981;
F-rich fluid, whereas those above intrusive centers may be Carten et al., 1988b), both estimates are within reason. Geo-
dominated by contributions from the Cl-rich fluid (R. B. logic evidence indicates that the Urad orebody formed in a
Carten, pers. commun., 1987). shallower environment than Henderson (Wallace et al., 1978,
Second, four vapor-rich fluid inclusions were observed in p. 364–365), so major uplift did not occur at Red Mountain
one sample for which BIO-KSP was the targeted assemblage concurrent with hydrothermal activity.
(Fig. 7). The same sample also contains the only fluid inclu- According to Carten et al. (1988b), high-temperature fluids
sion that appeared to homogenize by critical behavior. It is were at or above lithostatic pressures. Further, moderately
uncertain as to which assemblage these two types of fluid in- high temperature assemblages generally are associated with
clusions are related, because these two types did not occur in discontinuous, thin veinlets (Seedorff and Einaudi, 2004,
any other samples, including two others with the same target table 2), suggesting that pressures also may have been near
assemblage. This constitutes permissive evidence for phase lithostatic when they developed. Commencing with deposi-
separation during lower temperature evolution of the hy- tion of moderate-temperature assemblages, veins became
drothermal system, although there are no saline fluid inclu- more through going, and the upper limit of alteration mi-
sions with similar homogenization temperatures as the vapor- grated to higher levels during deposition of moderate- and
rich fluid inclusions in that sample. low-temperature assemblages (Seedorff and Einaudi, 2004,

FIG. 7. Histograms of all homogenization temperatures of fluid inclusions and probability histograms pertinent to their
geologic interpretation. The left side displays histograms of homogenization temperatures for samples with the target as-
semblage(s) that are described in the center-right. Histograms are arranged vertically according to the target assemblage(s),
from members of the moderately high temperature group at the top to the low-temperature group and propylitic alteration
at the bottom. Geologic data are summarized in columns along the right side. At the upper right corner, assemblages are
listed from left to right by groups, from low to high temperatures, inferred prior to fluid inclusion study. Bars associated with
the target assemblage(s) are marked by arrow(s). For each sample, an assemblage that occurs nearby is denoted by a bar,
with each bar consisting of as many as four boxes. The height of the bars qualitatively represents the geologic probability that
a given assemblage is responsible for inclusions shown in the histogram. Shaded bars denote assemblages that may have con-
tributed secondary fluid inclusions because those assemblages occur in veinlets nearby that, in the vicinity of the sample, are
younger than the target assemblage(s). Unshaded bars denote additional assemblages that may contribute fluid inclusions
because the host in that heating run is an igneous mineral, and thus assemblages that are both younger and older than the
target assemblage must be considered. One box (L) is shown if the sample occurs within the known limits of an assemblage
on a deposit scale (Fig. 2). A second box (50) also is present if at least one occurrence of the assemblage was logged in the
same 50-ft interval of core as the sample, and a third box (10) if the assemblage is present in the same 10-ft interval. A fourth
box (S) indicates that the assemblage is present in the hand sample that is the source of the fluid inclusion chip. There are
no data for assemblages nearby in the 10 and 50 rows (replaced by asterisks) for H-471-255 because this sample was not
within an interval logged by the author.

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 50 SEEDORFF AND EINAUDI

60
figs. 10, 12). This increase in fracture permeability may have
H - 499 - 295.2
BIO - KSP coincided with a transition from lithostatic to hydrostatic con-
Vein - filling quartz ditions (e.g., Gustafson and Hunt 1975; Fournier, 1999), al-
50
though it is possible that even some of the low-temperature
assemblages formed under a lithostatic regime. Geraghty et
40
al. (1988) calculated lithostatic pressures of approximately 0.7
to 0.8 kbars for the region near the tops of the principal min-
30
eralizing intrusions. The actual fluid pressure may have de-
<29 clined during deposition of the final, low-temperature assem-
blages if hydrostatic conditions were reached.
H - 074 - 24 Even at the highest possible estimated pressure (<1.0
60 TPZ - PY, SER - PY kbar), pressure corrections on homogenization temperatures
Vein - filling topaz
of fluid inclusions from Henderson fluids would be small,
50 particularly for the most saline inclusions (Potter, 1977). For
calculation of phase equilibria, uncorrected homogenization
40 temperatures are used, a pressure of 0.5 kbar is considered as
a first approximation for moderately high and moderate-tem-
30 perature assemblages, and the effect of declining pressure
<29
from this value is examined.
S A L I N I T Y (Wt. %)

40
Geochemical Evolution and
Plane B
(5 points) CX - 158 - 1416
Mass Transfer of Nonore Components
2 43
SER - PY
35 3 2 Quartz phenocryst Types of geochemical paths and means of illustration
Plane A cut by veinlet
30
(22 points) The mineralogy, sequence, and distribution of hydrother-
2 mal mineral assemblages, thermally calibrated by fluid inclu-
<29 sion results, mark the trail of geochemical evolution of hy-
drothermal fluids and provide qualitative insight into mass
transfer at Henderson. We describe two types of geochemical
CX - 93 - 814
35 SPHAL
paths with different frames of reference, one from the rock
Quartz phenocryst perspective and the other from the fluid perspective (see also
30 2 cut by veinlet Seedorff and Einaudi, 2004).
The rock perspective, with its coordinate system fixed in
<29 space, is useful when fluids are evolving over narrow intervals
of time and temperature. Conventional displays of phase
35 CX - 91 - 1059 equilibria, such as activity-activity diagrams, can be used to il-
GAR lustrate quasi-isothermal paths quantitatively from the rock
Quartz phenocryst
30 in GAR envelope perspective.
The fluid perspective, in contrast, is most appropriate for
<29
describing the evolution of fluids over longer times and dis-
200 250 300 350 400 450 500 550 600 650 tances and uses a coordinate system that follows the fluid.
HOMOGENIZATION TEMPERATURE (°C) Temperatures of fluids in porphyry systems range over many
hundreds of degrees Celsius, beginning above the solidus of
magmas, so deposit-scale geochemical paths are a challenge
to display. The first strategy is to plot temperature on one of
the axes of a diagram (sacrificing display of a chemical vari-
able) because the locations of phase boundaries shift with
FIG. 8. Temperature vs. salinity diagrams for selected fluid inclusion sam-
ples. Geologic data pertinent to interpretation and a key to symbols are con-
temperature (although the topology of the phase diagram
tained in Figure 7. Where a number also appears in a box, this indicates the may remain unchanged). Second, conventional activity-activ-
number of points associated with the symbol plotted at that location. All liq- ity diagrams may still be used quantitatively under certain cir-
uid-rich inclusions are simply plotted at the appropriate temperature, in the cumstances without sacrificing a chemical variable if dia-
manner of a histogram, below the horizontal line at the bottom of each dia- grams can be complexly stacked or contoured. Third, paths
gram; for the system H2O-NaCl-KCl, these would have salinities of less than
29 wt percent. For CX-158-1416, fields of points are outlined for obviously from the fluid perspective can be superimposed on the topol-
secondary fluid inclusions (many displaying negative crystal habits) that were ogy of the phase diagram, without labeling the values on the
assigned to two particular planes during petrographic examination made axes, if the purpose is to illustrate the succession of phase
prior to heating. Note that the salinity scale is condensed by 50 percent in the boundaries crossed. In this case, however, the directions of
upper two diagrams compared to the lower three. For samples illustrated
from the suite of assemblages above intrusive centers (bottom four dia-
the arrows have no meaning relative to a fixed set of axes in
grams), there is a general trend of decreasing temperature and decreasing an isothermal view; they have meaning only relative to the
maximum salinity in the sequence from top to bottom after geologic con- succession of phase fields crossed. We use all three types of
straints (Fig. 7) are considered. diagrams to display the polythermal geochemical evolution at

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 51

Henderson, where there are two principal deposit-scale fluid of these two evolutionary paths, it is assumed initially that the
trajectories to describe—one for each of the two suites of as- two paths had a common starting composition (dark circles of
semblages (Fig. 2). Figs. 9–10). A second family of paths (thin arrows) is shown
that begins at selected points along the deposit-scale evolu-
Paths on activity-activity diagrams tionary paths. The paths shown by thin arrows illustrate the
Figures 9 and 10 show deposit-scale evolutionary paths quasi-isothermal and -isobaric activity gradients during diffu-
(wide arrows) in activity-activity diagrams. Because the same sion of fluid from channel way to alteration front on the scale
assemblages were produced at high temperatures along each of an alteration envelope (centimeters in width), as recorded
by zoned alteration envelopes.
SUITES GROUPS OF ASSEMBLAGES The deposit-scale paths for both suites evolve from K-
MODERATELY
feldspar to topaz to sericite with time and decreasing tem-
HIGH HIGH MODERATE LOW perature (Fig. 9A-B). Hydrothermal fluids that evolve on the
Above intrusive centers flanks of the Seriate center follow the K-feldspar-topaz
H MH M L boundary, whereas fluids above intrusive centers cross the K-
On flanks of seriate center feldspar-topaz boundary at values of aF– ⋅ aH+ greater than the
decreasing temperature →
K-feldspar-topaz-sericite invariant point. After the fluids sat-
fluid evolution → urate with respect to topaz and then sericite, the two paths
QUASI-ISOTHERMAL AND -ISOBARIC REACTION PATHS
merge at low temperatures (not shown in phase diagrams) as
the fluids eventually reattain equilibrium with K-feldspar in
the host rocks. The paths associated with both suites of as-
X X'
toward fresh rock →
semblages provide the opportunity to develop zoned en-
velopes on single veins that contain inner topaz and outer
1-1' TPZ-PY//TPZ-PY/SER-PY/(FRESH) 4-4' TPZ-MT//TPZ-MT/SER-MT/(FRESH) sericite zones (paths 1-1' in Fig. 9A and 4-4' in B). Only deep
2-2' SER-PY//SER-PY/(FRESH) 5-5' TPZ-PY//TPZ-PY/GREEN BIO/(FRESH) fluids on the flanks of the Seriate center have ample opportu-
3-3' TPZ-MT//TPZ-MT/(FRESH) 6-6' SER-MT//SER-MT/(FRESH) nity to develop topaz-bearing alteration envelopes without an
7-7' GREEN BIO//GREEN BIO/(FRESH) outer sericitic envelope as relative values of aF- ⋅ aH+ remain
higher than in the regions above intrusive centers (e.g., path
3-3' in Fig. 9B).
A biotite field can be displayed if iron is added to the sys-
K2O-Al2O3-SiO2-HF-H2O tem (Fig. 9C-D). In high-temperature assemblages, early
Suite Above Intrusive Centers Suite on Flanks of Seriate Center QTZ-FL lacks biotite, whereas later QTZ-KSP-MO locally
contains brown biotite. At moderately high temperatures, the
TPZ potassic alteration path for fluids above intrusive centers only
+QTZ +QTZ MH
M 3
rarely reaches the K-feldspar-biotite boundary as it evolves
)→

a =1 M a =1
)→

H2O MH H2O
1 4 H
H+
H+

H TPZ 6 3'
.a
.a

2 1' 4'
F-

L
F-

L FIG. 9. Evolutionary paths of fluids on schematic activity diagrams. This

log (a
log (a

6' figure displays the contrasting paths for the two suites of assemblages and il-
2'
SER SER lustrates the similarity between the temporal sequence of assemblages (early
KSP to late) along small increments of a polythermal evolutionary path and the
KSP
A B spatial sequence of assemblages (proximal to distal) in a single zoned enve-
log (a a )→ log (a )→ lope. Polythermal paths here are diagrammatic because the absolute position
K+/ H+ K+/a H+ of the invariant point in activity space shifts as a function of temperature rel-
ative to a fixed origin. The topology of the diagram, which is all that is of in-
terest here, remains similar for various temperatures, although the diagram
was constructed at 400°C (within the range of moderate-temperature assem-
K2O-FeO-Al2O3-SiO2-HF-H2O blages). Wide arrows describe the geochemical paths of packets of fluid that
Potassic Sericitic evolve in space and time (the fluid perspective), with a concomitant decline
(± Transitional to Sodic) (± Rarely Transitional to Sodic) in temperature, for the two suites. Compositions of the initial fluids are pre-
Assemblages, Both Suites Assemblages, Both Suites sumed to be similar for the two suites of assemblages, although the fluids
evolve along different paths. Thin, numbered arrows show the quasi-isother-
mal and -isobaric activity gradients from vein filling toward alteration front
TPZ with fresh, K-feldspar–bearing wall rock, as deduced from the sequence of
+QTZ +QTZ TPZ mineral assemblages in zoned alteration envelopes. Slopes of the narrow
a =1 a =1 lines are schematic; they are drawn at shallow angles to aAl3+/a3H+, but the ac-
H2O H2O
)→

)→
FA

FA

BIO tual paths are unknown. A and B portray equilibria in the vicinity of the in-
H+

H+

M variant point involving K-feldspar (ksp), sericite (ser), and topaz (tpz), with
4 M BIO
.a

.a

1 separate diagrams for each suite. C and D depict equilibria involving K-

M 5
F-

F-

MH MH feldspar (ksp) or sericite (ser), biotite (bio), fayalite (fa), and topaz (tpz). Each
5'
log (a

log (a

KSP H 2 6 7 diagram contains paths for both suites, but C applies to potassic (±transi-
H SER 1' 4' tional to sodic) assemblages (i.e., aK+/aH+ sufficient to stabilize K-feldspar in-
2' 6' 7'
stead of sericite), whereas D shows sericitic (±rarely transitional to potassic
C D and sodic) assemblages (i.e., aK+/aH+ appropriate for stability of sericite in-
log (a 2 )→ log (a 2 )→
Fe2+ /a H+ Fe /a H+ stead of K-feldspar, andalusite, or pyrophyllite).
2+

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 52 SEEDORFF AND EINAUDI

K2O-FeO-Al2O3-SiO2-HF-H2O toward the topaz field (Fig. 9C). For fluids on the flanks of
the Seriate center, the path follows the K-feldspar-biotite uni-
a variant line toward higher aF– ⋅ aH+ (Fig. 9C).
+QTZ FA H2O = 1 During sericitic alteration (Fig. 9D), the path for fluids
2 )→

above intrusive centers is not well constrained in the iron-

B I O GREEN BIOTPZ-BIO-MT bearing system, but it must have evolved to values of
Fe2+ /a H+

BIO-KSP aFe2+/a2H+ that were low enough such that a fluid in the topaz
SER-MT
field (Fig. 9D) could develop an outer sericitic envelope that
ANDAL replaced both magmatic K-feldspar and magmatic biotite (re-
or TPZ-MT action path 1-1'). On the other hand, the path for fluids on the
log (a

PYROPH KSP
flanks of the Seriate center must have moved to higher values
of aFe2+/a2H+ relative to the topaz-biotite-sericite invariant
SER point in order to intersect the biotite field again. These fluids,
A while in the topaz field (Fig. 9D), developed zoned envelopes
with outer zones of either sericite (reaction path 4-4' with
log (a )→
K+/a H+ SER-MT) or biotite (reaction path 5-5' with GREEN BIO).
A projection illustrating aFe2+/a2H+ and aK+/aH+ (Fig. 9A)
K2O-Na2O-Al2O3-SiO2-H2O shows that the GREEN BIO assemblage, which does rarely
contain sericite, can be classified as a sericitic-type assem-
+QTZ TPZ-BIO-MT blage (Seedorff and Einaudi, 2004) because values of aK+/aH+
are appropriate for sericite, just as certain chlorite-bearing as-
a
H2O = 1
BIO-KSP
TPZ-MT
semblages can be classified as sericitic (Seedorff, 1991).
a )→

The difference in the geochemical paths of the two suites

Na+ / H+

ALBITE H probably can be accounted for largely by greater production

MH of H+ by fluids evolving above intrusive centers than by fluids
M
PA R A G SER-MT evolving on the flanks of the Seriate center. Fluid inclusion
L KSP data from high-temperature assemblages (Carten, 1987) sug-
ANDAL
log (a

or gest that concentrations of HCl, rather than H2S, probably

PYROPH SER are most responsible for that difference. Concentrations of K+
and Fe2+ in the fluid may have been similar in both suites.
B A field for albite appears upon consideration of the Na2O
log (a )→ component (Fig. 10B-C). Fluids above intrusive centers ap-
K+/a H+ pear to have evolved at lower aNa+/aH+ than fluids on the
flanks of the Seriate center. The path for fluids above intru-
K2O-Na2O-FeO-Al2O3-SiO2-HF-H2O sive centers misses the albite field. Fluids on the flanks of the
Seriate center straddle the albite-K-feldspar boundary at
+QTZ moderately high temperatures but leave the albite field upon
ALBITE forming the TPZ-MT assemblage, so the path reflects
a
H2O = 1 aNa+/aH+ values lower than the albite-K-feldspar-sericite in-
a )→

BIO-KSP
variant point (Fig. 10B). The path locally reaches the sericite-
Na+ / H+

albite boundary in the SER-MT assemblage (Fig. 10B) in the

FA

TPZ-BIO-MT rare cases where both muscovite and albite occur together.
MH The projection used in Figure 10C depicts equilibria involv-
TPZ-MT M ing topaz as well as K-feldspar, biotite, and albite. Path dif-
log (a

ferences in terms of aK+/aH+ and aNa+/aH+ (Fig. 10B) probably

T P Z + BI O result from slight contrasts in the directions of flow for the
T P Z + KS P
two fluids relative to the orientation of isotherms.
C
Mass transfer and topaz saturation
log (a 2 )→
Fe /a H+
2+
Figure 11 summarizes the mass transfer that occurred dur-
ing evolution of fluids associated with the two suites of as-
FIG. 10. Additional polythermal evolutionary paths on schematic activity semblages. The alkalis underwent a complex history of mass
diagrams, emphasizing suite of assemblages on flanks of Seriate center. See transfer. In the suite above intrusive centers, sodium proba-
Figure 9 for abbreviations for minerals other than andalusite (andal), pyro-
phyllite (pyroph), and paragonite (parag). Specific assemblages formed on bly was leached from the rock in all assemblages. On the
flanks of Seriate center are labeled. A. Path in terms of aK+/aH+ and aFe2+/a2H+. other hand, it is unknown whether there was net removal or
B. Paths for fluids on flanks of Seriate center and above intrusive centers in addition of sodium on the flanks of the Seriate center at mod-
terms of aNa+/aH+ and aK+/aH+. C. Equilibria involving K-feldspar, biotite, erately high temperatures because K-rich, K-Na, and Na-rich
topaz, and albite projected along the univariant line marking equilibria be-
tween topaz-K-feldspar and topaz-biotite (Fig. 9C), such that aF-⋅aH+ is fixed
alkali feldspars commonly are intergrown on a fine scale in a
for a given value of aFe2+/a2H+. The aK+/aH+ is set at a value sufficient to sta- variety of precursor mineral sites. At moderate and low tem-
bilize K-feldspar instead of sericite. peratures, sodium was removed from the rock on the flanks of

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 53

Suite of assemblages above intrusive centers Suite of assemblages on flanks of Seriate Center

Abbreviation DISTAL Abbreviation

Group of of
assemblage Components assemblage
F, (Fe), Mn, (S) transferred from
RHOD (Na?), (K?) fluid to rock
TEMPERATURE Merges with
F, Fe, (Pb), (Zn), Mn, S Components other suite
GAR Na, (K?) transferred from of low-
LOW

F, Fe, Zn, Pb, (Cu), S rock to fluid temperature

SPHAL Na, (K?) assemblages

F, Fe, S
PY - CLAY Na, (K?) F, Fe, (S)
Na, (K?) PO

F, Fe, (Mn), (S)

GREEN BIO
TEMPERATURE

F, Fe, S Na, (K?)

MODERATE

SER - PY
Na, (K?)
F, Fe
(Na?), (K?) SER - MT
F, Fe, W, S
TPZ - PY Na, K F, Fe
Na, (K) TPZ - MT
MODERATELY HIGH

(K?), F, Fe F, Fe
TEMPERATURE

TPZ - BIO -
MT - KSP Na ? MT

MOTTLED (K?), F F, (Fe), (Mo), ( S)

? BIO - KSP
KSP - QTZ Na, Fe
TEMPERATURE

QTZ - KSP - K, F, Mo, S K, F, Mo, S QTZ - KSP -

MO Na, Fe Na, Fe MO
HIGH

F, Si F
QTZ - FL Na, K ,Fe QTZ - FL
Na, K, Fe
PROXIMAL

Introduction of juvenile hydrothermal fluids at apices of stocks

+ +
+ +

FIG. 11. Schematic representation of mass transfer of nonore components and metals at Henderson. Single-headed ar-
rows represent mass transfer of components between fluids and rocks during evolution of fluids along two evolutionary paths
(shaded light and dark). The paths begin with injection of juvenile magmatic hydrothermal fluids and progress from proxi-
mal to distal products, diverging at higher temperatures and merging at low temperatures. The generalized evolutionary path
above intrusive centers is most applicable to the Henderson and Seriate centers, as some assemblages failed to form above
the Vasquez center.

the Seriate center. Above intrusive centers, potassium initially fluids that produced these assemblages followed a prograde
was leached at high temperatures in the QTZ-FL assemblage, thermal path (e.g., Hemley et al., 1980; Carten, 1986). Chess-
then added to the rock in the QTZ-KSP-MO assemblage, and board twinning, a characteristic of replacement of K-feldspar
may have been added in the MOTTLED KSP-QTZ and MT- by albite during sodium metasomatism (Carten, 1986, p.
KSP assemblages. At moderate temperatures, potassium 1502), has not been observed at Henderson. In contrast to the
must have been strongly leached in the TPZ-PY assemblage, sodic-calcic and sodic assemblages that formed deep in the
probably was slightly leached in the SER-PY assemblage Yerington porphyry copper system (Carten, 1986), the sodic
(White et al., 1981, p. 305), and may have been slightly plagioclase-bearing assemblages at Henderson contain K-
leached at low temperatures. The mass transfer of potassium feldspar and biotite; hence, they are assigned to a transitional
as a function of declining temperature appears to be qualita- potassic-sodic type of alteration (fig. 7 of Seedorff and Ein-
tively similar in the suite formed on the flanks of the Seriate audi, 2004). No magma was present to the deepest observed
center. levels of exposure at the time when these assemblages
The local presence of Na-rich feldspars in the suite formed formed; nonetheless, fluids may have been flowing toward
on the flanks of the Seriate center raises the possibility that the most recent intrusion. Because of the mineralogy and

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 54 SEEDORFF AND EINAUDI

space-time relationships, these fluids probably did not follow K2O-Al2O3-SiO2-HF-H2O

a strictly prograding thermal path, although they probably
were flowing at low angles to isotherms. Sodic hydrothermal TPZ SS
X T (C)
alkali feldspars, including ones of intermediate Na-K compo- F-TPZ
sitions, are reported by John (1989, p. 895, 898–899) in type
2 veins in the Park Premier system, and John (1989) con- 0.99 300
cluded that they, too, do not represent a prograding thermal TPZ
SS 350
path. 0.90
Effects of temperature and solid solution in topaz and 0.80
0.70 400
sericite on the evolutionary path are explicitly displayed in 0.60 KSP
0.60
Figure 12, which is otherwise equivalent to Figure 9A and B. -10
PYROPH SER-MT
This analysis, utilizing compositions of topaz and homoge- 0.70 SER-PY
nization temperatures from fluid inclusions, reveals that the ANDAL MUSCSS
entire path can be traced at nearly constant log aK+/aH+ (~3), 0.99 450
with the suite above intrusive centers following a path at
slightly lower aK+/aH+. 0.90
TPZ-PY
TPZ-MT, SER-MT,
To enter the topaz field from the K-feldspar field following 0.80 GREEN BIO
an isobaric path, a fluid must outrun an advancing front of 0.70
topaz stability (Fig. 12). Migration of invariant points to
higher values of aF– ⋅ aH+ with a decrease in temperature

Above
-15

Flanks
)→
from 600° to 300°C is even more pronounced at lower pres-
sures (Fig. 13). The effect of a decrease in pressure from 0.5

H+
to 0.3 kbars, which is dramatic above 350°C, is highly effec- 0.99 500

.a
tive at driving a fluid into the topaz field (Fig. 13). There is TPZ-BIO-MT

F-
geologic evidence at Henderson for a decrease in pressure 0.90
log (a 0.80
with evolution of the fluids (discussed above); decline in pres- MT-KSP

sure (overpressured lithostatic to lithostatic, or lithostatic to

hydrostatic) may have contributed to saturating the fluid with
respect to topaz. The pressure effect on K-feldspar-sericite -20
0.99 550
equilibria is minor (Fig. 13), indicating that a drop in tem-
perature, not pressure, promoted change from potassic to 0.90 BIO-KSP
sericitic alteration (Fig. 12). 0.80
MOTTLED KSP-QTZ
A fluid would have a higher probability of saturating with 0.99
respect to topaz if its initial fluorine content and its capacity 600
to generate hydrogen ion were high. High initial magmatic 0.90 QTZ-KSP-MO
fluorine contents at Henderson (Carten, 1987; Carten et al., QTZ-KSP-MO
1988b) probably are most responsible for evolutionary paths -25
that traverse from K-feldspar to topaz to sericite, i.e., evolve >600
on the K-feldspar-topaz side of the migrating invariant point ANDAL
QTZ-FL, QTZ-KSP-MO

topaz-sericite-K-feldspar. In contrast, the paths for topaz- KSP

bearing deposits that are less fluorine rich than Henderson,
0 2 4 6
such as Butte, Montana (Meyer et al., 1968; Howard, 1972),
log (a a )→
generally evolve from K-feldspar through sericite, andalusite, K+ / H+
pyrophyllite, and/or kaolinite before saturating with respect
to topaz, i.e., tend to evolve on the K-feldspar-sericite side of Above intrusive centers
the invariant point (Seedorff, 1986). Flanks of Seriate center
Fluids on the flanks of the Seriate center entered the
topaz field at an earlier stage in their evolution than fluids FIG. 12. Temperature effect on geochemical evolutionary paths. Figure is
produced by stacking phase diagrams for multiple temperatures. Locations of
above intrusive centers (Figs. 2, 9–10, 12). One might ex- points that are plotted along the evolutionary paths for fluids that formed the
pect, on the basis of the aK+/aH+ values of the two paths two suites of mineral assemblages (Fig. 2) are based on homogenization tem-
(Figs. 9A-B, 12), that the fluids on the flanks were less, peratures of fluid inclusions and analyzed compositions of topaz from various
rather than more, acid than fluids above intrusive centers; assemblages (table 6 of Seedorff and Einaudi, 2004). Points are labeled with
further, these deeper fluids would tend to reach lower pres- assemblages appropriate to the temperatures shown. The quantitative paths
shown here in the stacked diagrams are equivalent to the schematic paths
sures later, rather than sooner, compared to the other suite. shown in the single diagrams of Figures 9A-B. Abbreviations are as in Figures
Processes that operated at moderately high and moderate 2, 9–10. Diagram uses proton avoidance model for solid solution in topaz
temperatures, therefore, probably cannot explain the earlier (Barton, 1982), ideal site solution model for activity of hydroxyl muscovite, an
appearance of topaz on the flanks of the Seriate center. This average composition appropriate for sericite/muscovite from Henderson, and
assumes unit activity and equilibrium state of order of K-feldspar. Diagram is
implies that the paths of the two fluids began to diverge at plotted at PT = PH2O = 0.5 kbar in the presence of quartz, activity of water = 1,
high temperatures or that the fluids on the flanks of the cen- and activity of OH muscovite in muscovite solid solution = –0.5. The compo-
ter may have been preferentially enriched in fluorine at the sition of topaz solid solution at invariant points is insensitive to pressure.

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 55

P = 0.3 kb P = 0.5 kb outset. The latter hypothesis is consistent with fluid inclu-
300 sion results from high-temperature assemblages (Carten,
300 1987).
TPZSS KSP TPZSS KSP Fluorine was continuously added to wall rocks along the
350 entire length of the evolutionary paths of fluids forming both
350
PYROPH
PYROPH suites of assemblages (Fig. 11), as fluorite was newly forming
-10 MUSCSS -10 PYROPH in every assemblage and significant fluorine was being fixed in
PYROPH

400
numerous other hydrothermal phases, including topaz, mica,
and garnet (Fig. 2). Although migration of hydrothermal
400 ANDAL fluids and their continual reaction with wall rocks caused
450 fluorine to be widely dispersed, geochemical analyses indicate
that the strongest fluorine enrichment is inside the Mo
MUSCSS orebody and that, on the deposit scale, F content varies di-
-15 -15
rectly with Mo content (Bright, 1974).
Mineralogic evidence indicates that iron was leached as hy-
ANDAL T = 500 C drothermal fluids evolved at high to moderately high temper-
atures—in wall rocks with low total iron contents. Above in-
trusive centers, iron was leached during formation of the
QTZ-FL, QTZ-KSP-MO, and MOTTLED KSP-QTZ assem-
)→

-20 -20 blages, as evidenced by destruction of magmatic magnetite

and biotite and general absence of hydrothermal iron-bearing
H+

550
phases; iron was first added to the rock as magnetite in the
.a

MT-KSP assemblage and subsequently was fixed mostly as

F-

pyrite (Fig. 11). On the flanks of the Seriate center, leaching

600
log (a

of iron terminated earlier in the evolutionary sequence (Fig.

KSP
-25 -25
ANDAL 11), as magnetite and Fe-bearing silicates began to be de-
posited in the BIO-KSP assemblage and were deposited in
450 abundance in the TPZ-BIO-MT and TPZ-MT assemblages
0 2 4 6 (Fig. 2).
log (a a )→ On the scale of an individual vein, it is obvious from hand-
K+ / H+ specimen and petrographic observations that wall-rock reac-
tions between fluid and feldspar phenocrysts were important
-30 to precipitation of magnetite and pyrite, in a manner similar
T = 500 C to the promotion of molybdenite deposition at high tempera-
tures by wall-rock reactions between fluid and K-feldspar
(Carten et al., 1988b). In turn, magnetite appears to have
played a role in fixing sulfur in the rock, because iron sulfides
(pyrite, pyrrhotite) that were deposited at intermediate to
deep levels in the system at moderate and low temperatures
-35 550 were localized by interaction of fluids with precursor hy-
drothermal magnetite.
Oxidation and sulfidation states
600
Although the Henderson deposit does not contain a wealth
KSP of minerals that are useful for specifying oxidation and sulfi-
-40 ANDAL
dation states of fluids, coexisting minerals in assemblages
(Fig. 2), when coupled with information on evolutionary
0 2 4 6 paths and temperatures from fluid inclusion studies (Table 1),
nonetheless provide important constraints (Fig. 14). Note
log (a a )→
K+ / H+ that molybdenite does not occur in equilibrium with pyrite in
either suite of assemblages (Fig. 2), although the two miner-
als commonly occur together in the same sample due to su-
perimposed events at Henderson and were coprecipitated in
many other porphyry deposits. For the suite above intrusive
centers, pertinent observations are the following: pyrrhotite is
FIG. 13. Pressure effect on topaz equilibria. All conditions, assumptions, not present; the transition from magnetite- to pyrite-bearing
and abbreviations of Figure 12 apply except for differences in pressures. If a assemblages (at inception of deposition of the TPZ-PY as-
point within the K-feldspar field at 400°C and the specified values of aK+/aH+
and aF-⋅aH+ were subjected to an instantaneous drop in pressure from 0.5 to
semblage) took place at approximately 450° to 500°C;
0.3 kbars, its position would then lie well inside the stability field of topaz hematite locally accompanies pyrite in the PY-CLAY and
solid solution. SPHAL assemblages; sphalerite occurs with chalcopyrite and

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 56 SEEDORFF AND EINAUDI

Space-Time Constraints on
Introduction and Deposition of Metals
-0
Mapped alteration-mineralization relationships that can be
correlated in time across much of the deposit, as documented
Above intrusive by Carten et al. (1988b) and Seedorff and Einaudi (2004),
uid

PY
iq centers
place important constraints on the timing of introduction and

M HM+
rL
lfu
Su deposition of Mo, W, Pb, Zn, Cu, and Mn at Henderson, as

T
Flanks of
PY
Seriate center shown in Figures 15 and 16.
PY
FS
→

HM
-4 Carten et al. (1988b) demonstrated that juvenile hydro-
FS

thermal fluid was introduced at high temperatures and that

Mo was deposited in numerous cycles, each corresponding to
PY

emplacement and crystallization of a mineralizing stock.

2

S
log f S

+F
PO

PY M Molybdenum largely remained in solution through formation

H

WS T
of the QTZ-FL assemblage, but most of the Mo that was pre-

+M
HM MT
FS PO cipitated was deposited in the assemblage QTZ-KSP-MO
PO
-8
(Figs. 2–4, 11, 15A-B, E, 16).
The metals deposited at moderate and low temperatures
PO
Fe
HM WS were precipitated principally from fluids in assemblages that
PY
T

FS MT PO formed above intrusive centers, which were more saline and

M
M

followed the more oxidized evolutionary path (Table 1; Figs.

FS H

11, 14). Because of constraints provided by spatial correlation

-12
of temporal events at Henderson (Seedorff and Einaudi,
300 400 500 600 700 800 900
2004), W was introduced at high temperatures by each miner-
Temperature (C) →
alizing stock of the first two intrusive centers and remained in
FIG. 14. Sulfidation states of fluids that formed two suites of assemblages solution through formation of all high- and moderately high
at Henderson. Paths assume similar, but not identical, starting compositions temperature assemblages, with minor exceptions (Fig. 2).
(see text) and show contrasting evolutionary paths of fluids evolving above in-
trusive centers versus on the flanks of the Seriate center. Paths are con- Tungsten was deposited primarily in the moderate-tempera-
strained to pass through regions outlined by dots (see text). Short labeled ture assemblage TPZ-PY in one major event prior to intrusion
bars within various fields show phases that can coexist in those fields. Abbre- of stocks of the Vasquez center, but deposition took place si-
viations: Fe = native iron, FS = ferrous sulfate, HM = hematite, MT = mag- multaneously in two zones (Seedorff and Einaudi, 2004, table
netite, PO = pyrrhotite, PY = pyrite, WS = wustite. Sulfidation reactions cal-
culated from Barton and Skinner (1979).
7), one each over the Henderson and Seriate intrusive centers
(Figs. 5, 15C). The paucity of moderately high and moderate-
temperature assemblages (and thus W) in the Vasquez center
remains problematic (see Seedorff and Einaudi, 2004).
pyrite in the SPHAL assemblage; and rare barite has been ob- Similarly, Zn, Pb, and Cu were introduced at high temper-
served in the SPHAL assemblage (but only in occurrences atures by each mineralizing stock, and time lines suggest that
from high levels in the deposit). these metals remained in solution, with minor exception (Fig.
For the suite on the flanks of the Seriate center, magnetite- 2), through formation of all high-, moderately high, and mod-
bearing assemblages are relatively abundant, and pyrrhotite erate-temperature assemblages and certain low-temperature
locally occurs at the transition from magnetite- to pyrite-bear- assemblages (Fig. 11). The metals Zn, Pb, and trace Cu were
ing assemblages (Fig. 2). The temperature of deposition of deposited primarily in the low-temperature assemblage
the PO assemblage can be estimated, though only indirectly SPHAL in one event after all 12 stocks were emplaced but in
through its age relative to other assemblages whose tempera- three discrete zones (Figs. 15F, 16; Seedorff and Einaudi,
tures are known (Table 1), as 350° to 400°C. The first deposi- 2004, table 7), one each over the Henderson, Seriate, and
tion of pyrite-bearing assemblages (PY-CLAY) along this evo- Vasquez intrusive centers. The precipitation of galena and
lutionary path was at approximately 350°C. Although the two sphalerite only at low temperatures is expected from the sol-
suites merged at low temperatures, the pyrite- and locally ubility relationships of Pb and Zn (Hemley et al., 1992).
hematite-bearing assemblages that formed at low tempera- Nonetheless, the high salinities of the associated fluids (Table
tures were deposited in relatively low abundances at interme- 1) and discreteness of the three zones—in spite of their si-
diate to deep levels of the deposit (along the flanks of the Se- multaneous formation—are remarkable.
riate center and in the vicinity of the Vasquez center) In common with the other metals, Mn was introduced at
compared to above the Henderson and Seriate centers. high temperatures by each mineralizing stock. Although
These constraints imply that the evolutionary path of fluids minor Mn was fixed in micas in various assemblages formed
on the flanks of the Seriate center was more reduced in terms at higher temperatures, the low-temperature assemblages
of sulfidation and oxidation states than the path of fluids GAR and RHOD are the most important hosts of Mn (Figs.
above intrusive centers (Fig. 14). The more reduced path also 2–4, 11; see also Seedorff and Einaudi, 2004, table 6). There
evolved at a slightly higher aK+/aH+ (see above). Both of these is a single zone of concentration of the GAR assemblage (Fig.
trends imply a greater role for wall-rock buffering on the 15G), which Seedorff and Einaudi (2004) consider is proba-
flanks of Seriate. bly related to evolution of fluids from the Henderson center.

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 57

The RHOD assemblage is widely distributed, forming a pat- inability to identify unambiguously those fluid inclusions that
tern reminiscent of the distribution and abundance of the are related to the geologic event of interest likely is a major
SPHAL assemblage in three zones, although less clearly de- cause of variability in homogenization temperatures, although
fined than those of the SPHAL assemblage (Figs. 3–4, 15G). some workers have downplayed this possibility (Ahmad and
The RHOD assemblage was deposited in one event after all Rose, 1980, p. 242; Bloom, 1981, p. 1915–1916).
12 stocks were emplaced, immediately following deposition Samples—even those as small as thin section billets—from
of the GAR assemblage, but from fluids that contained less porphyry deposits generally contain mineralogical and tex-
than 29 wt percent NaCl equiv (Table 1). tural evidence of two or more events, even when samples
chosen for fluid inclusion study are selected with great care
Assessing the Possibility of Recycling Ore Components (Fig. 7). Hence, a cloud of uncertainty hovers over tying any
Early-deposited metals conceivably can be hydrothermally fluid inclusion measurement to a specific geologic event. On
leached, concentrated in the fluid, and reprecipitated where geologic grounds it can be argued—as is done here for some
there is extensive spatial overlap of different mineral assem- samples—that all of the fluid inclusions measured in a given
blages in a single, evolving hydrothermal system or where sample could be related to later, commonly lower tempera-
there is extensive overlap of two temporally distinct, geneti- ture, events rather than the targeted assemblage (Fig. 5,
cally unrelated hydrothermal systems. Considering the multi- Table 1). Because many measured fluid inclusions may not
plicity of mineralizing intrusions at Henderson, the possibility represent the fluid of interest, early, high-temperature alter-
that the ore metals (Mo, W) that were deposited prior to em- ation-mineralization events in some porphyry deposits proba-
placement of the final intrusive center, Vasquez, were recy- bly formed at much higher temperature than those that have
cled warrants evaluation. been inferred by other workers (e.g., Climax: Hall et al., 1974,
At Henderson, textural observations indicate that neither table 5). The underlying causes of preserving, modifying, or
molybdenite grains, which mostly are related to the assem- destroying fluid inclusions in porphyry-related deposits in
blage QTZ-KSP-MO, nor wolframite grains, which occur general are imperfectly known.
largely in the assemblage TPZ-PY, are generally affected
where superimposed by alteration envelopes related to Origin of sericitic and intermediate argillic alteration
younger veinlets. Nonetheless, centimeter-scale redistribu- The potassic-sericitic transition has a rich mineralogic
tion of molybdenum is locally observed with the moderately record at Henderson compared to many other porphyry-re-
high temperature, spatially restricted, assemblage MOT- lated deposits (e.g., presence of feldspars, micas, and topaz,
TLED KSP-QTZ (Fig. 17A) and even more rarely where all of variable composition). This record permits closer mon-
earlier molybdenite grains are overprinted by exceptionally itoring of geochemical conditions across this transition at
intense versions of the moderate-temperature assemblage Henderson than does the mineralogy of Transitional-stage
TPZ-PY (Fig. 17C-D). Most lower temperature assemblages quartz sulfide B veins at many porphyry copper deposits. In-
contain no molybdenite (Fig. 2), and collectively they con- terpretations of the onset of sericitic alteration generally call
tain a very small fraction (<0.1 vol %) of the molybdenite in on the incursion of low-temperature, low-salinity meteoric
the entire deposit. Likewise, the patterns of abundance of water (Sheppard et al., 1971; Hall et al., 1974; Gustafson and
younger alteration types show no affect on molybdenite Hunt, 1975; Mutschler et al., 1981; Westra and Keith, 1981;
grade patterns, on the scale of single 10-ft assay intervals or Beane, 1983). Some invoke quasi-isothermal changes in
the scale of the deposit (Figs. 3–4). One of the most clear aK+/aH+ of an evolving fluid (Beane and Titley, 1981, p. 260)
cases is where isopleths of the greatest abundance of the and others call upon renewed influx of juvenile magmatic flu-
TPZ-PY assemblage on the 480-H section cut across molyb- ids, albeit of a different character than earlier juvenile fluids
denite grade isopleths at high angles without any change in (Hedenquist et al., 1998; Muntean and Einaudi, 2001, fig.
molybdenite grade in an area with grades >0.7 percent 17). These interpretations are not applicable to Henderson,
MoS2 (compare Seedorff, 1988, figs. 8, 16, near 63E and where phase equilibria suggest that hydrothermal fluids fol-
elev 7,700 ft). Thus, there is no evidence of either deposit- lowed essentially constant values of aK+/aH+ and that the
scale leaching or reconcentration of molybdenum and tung- potassic to sericitic transition largely was promoted by a de-
sten at Henderson. cline in temperature. Furthermore, fluid inclusion results in-
dicate that fluids that evolved above intrusive centers were
Discussion and Application to the saline during sericitic alteration and remained saline into in-
Origin of Porphyry Systems termediate argillic alteration. This persistence of high-salinity
fluids suggests that Henderson is likely among the most mag-
Geologic significance of fluid inclusion data matic water-dominated porphyry systems documented to
Early veins in porphyry systems, which have textures and date and that incursion of meteoric water probably was not an
mineral assemblages that are indicative of high (>500°C) important factor in the potassic to sericitic transition (which is
temperatures, contain fluid inclusions of inferred primary ori- supported by reconnaissance stable isotope analyses; M. Bar-
gin that commonly show a wide spread in homogenization ton and E. Seedorff, unpub. data, 1989).
temperatures from >550° to <350°C (e.g., Ahmad and Rose, The role of magmatic water in late alteration-mineraliza-
1980, fig. 6; Bloom, 1981, fig. 2; Bowman et al., 1987, fig. 6). tion processes in porphyry deposits may currently be under-
Numerous possible explanations for this variability have been stated (Hedenquist et al., 1998; Zhang et al., 1999; Ulrich et
offered (e.g., Bodnar and Beane, 1980, p. 883–884; Ahmad al., 2001; Harris and Golding, 2002). There may be diverse
and Rose, 1980, p. 239). This investigation indicates that the origins of sericitic and intermediate argillic alteration among

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 58 SEEDORFF AND EINAUDI

different types of porphyry deposits and between different Degree of recycling of ore components
examples of each type, in part depending on timing of ingress
of external fluids. The mineralogy of Henderson, its moderate Centimeter-scale redistribution of copper inside sericitic
sulfide content, abundance of halite daughter minerals in and advanced argillic envelopes is observable in most por-
fluid inclusions related to sericitic alteration, and lack of evi- phyry copper deposits, but the process rarely has been proven
dence for high sulfate content imply that Henderson was a to be a significant ore former at the deposit scale, in part be-
relatively low sulfate, high chloride, fluoride-bearing mag- cause alteration envelopes of given vein sets commonly do not
matic hydrothermal system. Sericitic alteration at Henderson sufficiently overlap and coalesce. The most convincing case
may be regarded as the chloride-fluoride fluid end member for remobilization has been made at Butte, based on the geo-
among porphyry deposits, which generated only a moderate logic relationship (e.g., Brimhall, 1979, fig. 13, p. 582) and sub-
volume of sericitic alteration. sequent lithologic analysis and theoretical modeling (Brimhall,

WEST EAST
52N-N63E-58N Section
Elev., Ft
n Mo
10,000 ai Seriat e Ore Zone
nt Wt %
ou Top of visible MoS2 4 East Lobe Shell
dM 5 Seriate Shell
Re molybdenite > 0.7
0.5 - 0.7 6 Ruby Shell
0.2 - 0.5
0.1 - 0.2 Top of visible 7 Nystrom Shell
2 < 0.1 molybdenite
4
W
Mo Henderson 5 W
3 Or e Zone
1 6 S
1 Phantom Shell
7 H
H 2 Henderson Shell
3 Primos Shell H
S
7,000 0 meters 500
480H
50E BEND 60E BEND 70E A B C

Pb-Zn

Mo
Vasquez Or e Zone
SER-PY 8 Vasquez Shell
SER-PY
Pb-Zn

H H
S H S
S

8 Pb-Zn

V V

D E F

Panel A Panel G Mo Pb-Zn

Pb-Zn Pb-Zn
Mn Mn

SER-PY
SER-PY
W Pb-Zn W Pb-Zn
Mn Mn
H
S
Mo Mo
Mo Mo
H S

Mn Mn
Pb-Zn Mo Pb-Zn
V Mo
V

G H I

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 59

1979, 1980; Brimhall and Ghiorso, 1983; Woitsekhowskaya and Timing of magmatic volatile fluxing into
Hemley, 1995) that demonstrate the thermodynamic validity the environment of deposition
and mass-transfer efficacy of such a process in forming Main-
stage ore by hypogene dissolution, deposit-scale transport, and Inspired by numerical models of magmatic fractionation
redeposition of pre-Main–stage Cu. processes (e.g., Candela, 1989; Cline and Bodnar, 1991), nu-
Evidence is lacking for either leaching or deposit-scale merous recent authors have called upon varying compositions
reconcentration of Mo or W by any younger assemblages at of progressively evolved juvenile magmatic hydrothermal flu-
Henderson (Fig. 17). The contrasting importance of hydro- ids to account for different hydrothermal mineral assem-
thermal recycling of metals at Butte versus Henderson can blages or veins formed over time. For instance, Dilles and
be rationalized on two accounts. First, the metals deposited Proffett (1995) proposed that multiple influxes of juvenile flu-
relatively early and at high to moderate temperatures at Hen- ids with variable initial compositions may account for differ-
derson, Mo and W, are less soluble at moderate temperatures ences in metal ratios in successive vein generations within the
than is Cu (e.g., Wood et al., 1987; Wood and Vlassopoulos, same intrusive center at the Ann-Mason porphyry copper
1989; Wood and Samson, 1998); indeed, molybdenite appar- deposit.
ently was inert at Butte (Brimhall, 1979, p. 582). Second, the Alternatively, such variations might be explained by evolu-
fluids at Henderson and many other porphyry-related de- tion of fluids within the environment of deposition, without
posits worldwide did not evolve to conditions characteristic of new influxes of juvenile fluid. Notwithstanding the conflicting
advanced argillic alteration (Fig. 12), which, even for Cu, may interpretations of the mechanism for volatile concentration
be required for effective leaching and redeposition of earlier and initial Mo concentration of magmas and fluids in por-
deposited metals (Brimhall and Ghiorso, 1983; Brimhall, phyry molybdenum deposits (Carten et al., 1988a, b; Keith
1999). and Shanks, 1988; Lowenstern, 1994; Shinohara et al., 1995),

FIG. 15. Seven, nearly instantaneous and two cumulative time panels, showing development of metal zones on bent sec-
tion 52N-N63E-58N, emphasizing decoupling of introduction of components by juvenile magmatic hydrothermal fluids re-
leased from various stocks and deposition of the metals Mo, W, Pb-Zn, and Mn. Compare to present-day distribution pat-
tern of Figure 4. Panels A through G represent a sequence of fairly narrow time intervals. Filled black circles in panels A, B,
and E correspond to centers of ore shells formed by each mineralizing stock (numbered); sizes of filled black circles are
scaled to Mo content of ore shells. Panels A, B, and E show introduction of fluids at high temperature from the apex of each
intrusion; directions that fluids were injected for the principal mineralizing intrusion in each intrusive center, based on ori-
entation and abundance of high-temperature veins, are shown by open white arrows. Juvenile magmatic hydrothermal flu-
ids were sourced from individual stocks of the three intrusive centers but coalesced at high to moderately high temperatures
into more diffusely defined reservoirs where fluids were reacting with rocks about the three centers, Henderson (H), Seri-
ate (S), and Vasquez (V). Panels C, D, F, and G are a series of snapshots that capture the location of the reservoirs, which
migrated slowly over time concurrent with evolution of fluids in temperature and composition and formed zones of concen-
tration of other metals as temperature declined. Open symbols of various shapes, filled with letter abbreviations of elements,
are placed at the center of each metal zone, as in Figure 4. The distribution of the SER-PY assemblage is inserted in its
proper temporal position between W and Pb-Zn to provide continuity of spatial patterns because of relatively large time gap
between deposition of W and Pb-Zn. A. Mo zone for Henderson intrusive center, showing upper limit of molybdenite. This
Mo zone is a composite feature produced by successive, discrete periods of introduction of metals by successively emplaced
stocks (primarily Phantom, Henderson, and Primos; contributions from Berthoud and Arapaho are negligible), with forma-
tion of each stock’s ore shell prior to emplacement of next stock. B. Mo zone for Seriate intrusive center, showing upper limit
of molybdenite. Seriate ore zone was produced by successive, discrete periods of introduction of metals and deposition of
Mo upon emplacement and cooling of East Lobe, Seriate, Ruby, and Nystrom stocks. C. Essentially simultaneous deposition
of two, partially coalesced W zones, one each related to Henderson and Seriate centers. D. Distribution of two, partially co-
alesced zones of concentration of the SER-PY assemblage that formed essentially simultaneously. E. Mo zone for Vasquez
center, produced almost solely by introduction of metals and deposition of Mo upon emplacement and cooling of Vasquez
stock (negligible contributions from the Dailey and Ute stocks, whose locations are poorly known, are not shown). F. Depo-
sition of three, remarkably distinct Pb-Zn zones, one each related to the Henderson, Seriate, and Vasquez centers. These are
interpreted to have formed essentially simultaneously, as isotherms collapsed across the three reservoirs of evolved magmatic
hydrothermal fluids. G. Deposition of three, partially coalesced Mn zones. Highest Mn zone, interpreted to be related to the
Henderson center, is a composite of subequal contributions from the GAR and RHOD assemblages; note that the RHOD is
superimposed on the GAR and that on the eastern side of the section the upper limit of the younger RHOD assemblage is
below the upper limit of the GAR assemblage. Two lower Mn zones, related to the Seriate and Vasquez centers, are related
primarily to the RHOD assemblage. All three RHOD zones formed essentially simultaneously. H. Time-integrated view
showing inferred flow paths of fluids. To aid visualization of the two-dimensional migration paths of fluids that deposited the
various metal zones through time, the labels for each zone are linked by lines, with arrows showing the order in which the
patterns developed, one path for each intrusive center. The Henderson path changes little during formation of the Mo and
W zones, then migrates upward as the SER-PY assemblage is formed, then farther upward and easterly until the Pb-Zn zone
formed, then descended slightly as the Mn zone formed during deposition of first the GAR and then the RHOD assemblage.
The Seriate path migrates upward from Mo to W to SER-PY—although not as much as in Henderson, then collapses down-
ward as the Pb-Zn and Mn zones form. The Vasquez patterns are weakly developed and show minimal migration. I. Sum-
mary diagram showing sites of introduction of fluids and metals and deposition of Mo at high temperature (from panels A,
B, and E) and deposition of a representative low-temperature zone (Pb-Zn from panel F), emphasizing the similarity in the
shapes of metal zones formed at low temperature with the shapes of the high-temperature ancestors from which they
evolved. The Henderson patterns are displaced from, but broadly mimic the shape of, the ore zone of the Henderson cen-
ter. The Seriate metal patterns tend to retain the donkey ears shape of the ore shell related to the Seriate stock. The Vasquez
patterns are crudely domal.

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 60 SEEDORFF AND EINAUDI

A. HENDERSON
SERIATE
VASQUEZ
Mo
Mo
Mo

HIGH
Intense Potassic
(± Silicic)

MODERATELY
HIGH
Less Intense Potassic Less Intense Potassic
Transitional
Potassic - Sodic
Less Intense
TEM PER ATURE

Potassic
Topaz-Bearing Sericitic
MODERATE

(~ Transitional Stage) W Transitional

SE Sericitic - Sodic
R
IAT
Sericitic
Fla
E

nk Pyrrhotite
LOW

VASQUEZ
s
Ab

HE
ov

ND Pb-Zn
e

Intermediate Argillic
ER
SO
N
Carbonate
Mn

FLUID EVOLUTION (~TIME)

B. Carbonate

Intermediate Argillic

Topaz-Bearing Sericitic
(~ Transitional Stage)

Potassic Pb-Zn Mn
500°

500°C

Mo
200°C
300°C
C

400°C

W
Mn
SPACE (elevation)

Mo Pb-Zn
W
Sericitic

Intense Potassic
(± Silicic)

Mo Pb-Zn Mn
Transitional Potassic
200°C

Sericitic - Sodic
300°C
400°C
500°C

Transitional
Potassic - Sodic

early TIME late

FIG. 16. Simplified evolutionary tree and space-time diagrams for Henderson, showing decoupling of the introduction of
components by juvenile magmatic hydrothermal fluids by various stocks and successive deposition of the metals Mo, W, Pb-
Zn, and Mn. Diagrams are recast from figures 12 and 13 of Seedorff and Einaudi (2004), with conversion of assemblages to
alteration types in both diagrams and addition of inferred temperature contours based on fluid inclusion temperatures of this
study. A. Evolutionary tree diagram shows the geochemical evolutionary paths, keyed to alteration types, and various metal
depositional events. Inset shows general trajectory of fluids in each intrusive center. B. Space-time diagram shows evolution
of mineral assemblages along a vertical line in the center of the hydrothermal system along cross section 52N-N63E-58N,
showing inferred flow paths of fluids and formation of the multiple spatial zones: numerous for Mo, two for W, and three
each for Pb-Zn and Mn. Note that multiple zones of metal concentration of metals deposited at moderate to low tempera-
tures (W, Pb-Zn, and Mn) formed during essentially one depositional event for each metal.

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 61

A B

1 cm
1 cm

C D
1 cm 1 cm

FIG. 17. Textural evidence regarding possible remobilization of molybdenum, from photographs that show effect of su-
perposition of the MOTTLED KSP-QTZ and TPZ-PY assemblages on preexisting molybdenite deposited in earlier veinlets
related to the QTZ-KSP-MO assemblage. Host rocks in all photographs are Urad porphyry. Medium-gray areas in all sam-
ples are quartz; bright white mineral in A is K-feldspar; in B, C, and D, topaz. A. MOTTLED KSP-QTZ assemblage (sam-
ple H-268-142), showing several dark quartz-molybdenite veinlets (one is aligned with two arrows); note that the earlier vein-
lets are no longer continuous, especially in areas of abundant secondary K-feldspar related to formation of the later
MOTTLED KSP-QTZ assemblage. Certain preexisting molybdenite grains are slightly coarser grained (closer to upper
arrow), and a few new molybdenite grains are disseminated in the patches of K-feldspar (e.g., in center at left edge). These
textures are interpreted to indicate local recrystallization of molybdenite and centimeter-scale remobilization and reprecip-
itation of molybdenum during formation of the MOTTLED KSP-QTZ assemblage. B. TPZ-PY assemblage (sample H-448-
440.3): a series of sheeted pyritic, wolframite-bearing veinlets parallel to long axis of photograph, cutting and offsetting an
earlier quartz-molybdenite veinlet (roughly aligned with two white arrows). The sheeted veinlets probably originally had
inner envelopes of TPZ-PY and outer envelopes of SER-PY, but the entire rock has been converted to the assemblage TPZ-
PY, probably due to coalescence of the inner envelopes. The sheeted veinlets do not contain molybdenite, and there is no
evidence of dissolution of molybdenum from the earlier quartz-molybdenite veins, although the grain size of molybdenite
may have been increased by recrystallization in the upper two-thirds of the sample. C. TPZ-PY assemblage (sample 82-213):
rock almost totally recrystallized to quartz + topaz + pyrite + fluorite and minor wolframite and ilmenorutile, with a tendency
to form monomineralic domains. Samples such as these are rare, i.e., volumetrically insignificant. This rock presumably is
the product of further fluid-rock interaction of a rock similar to the one shown in B with a fluid stable with the TPZ-PY as-
semblage. Corners of rectangle (white) show area enlarged in (D). D. TPZ-PY assemblage (sample 82-213, close up): en-
largement of (C), showing local disseminations of molybdenite (arrows), probably from dissolution and reprecipitation of
molybdenite on the scale of a hand specimen.

field relationships at Henderson documented by Carten et al. had crystallized downward to the lowest layer of unidirec-
(1988a, b) regarding the introduction of components and tim- tional solidification textures only ~200 m below the apex of
ing of formation of high-temperature Mo-bearing veins are each intrusion. The rock beneath the last unidirectional solid-
clear: fluxing of magmatic volatiles into the environment of ification textures layer has no aplitic groundmass, is hypid-
deposition must have been nearly instantaneous. Introduc- iomorphic granular, and is remarkably fresh and free of veins
tion of components was inversely proportional to the level of (Carten et al., 1988b).
crystallization of the stocks—greatest for crystallization of the Temporal relationships established at Henderson imply
apex of the stock where brain rock is present (e.g., Carten et that all metals contained in lower temperature assemblages
al., 1988b, Figs. 9–10) and complete by the time each stock (e.g., W, Pb, Zn, and Mn) were introduced synchronous with

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 62 SEEDORFF AND EINAUDI

Mo, as discussed above (Fig. 16). An influx of a W- and F- abundances there than above the Henderson and Seriate cen-
rich fluid—distinct from the fluids that produced Mo ore ters (Fig. 3; Seedorff and Einaudi, 2004). Initiation of the
shells—to form the wolframite-bearing TPZ-PY assemblage Vasquez center coincides with a district-wide shift in compo-
and related W halo at Henderson can be ruled out, as no ev- sition of intrusive rocks from the potassic series to the sodic
idence has been observed that juvenile magmatic hy- series of Carten et al. (1988b, p. 276-284).
drothermal fluids were entering the environment of deposi- The near absence of moderately high and moderate-tem-
tion when the most abrupt shift in the Mo/W ratio of veins perature assemblages above the Vasquez center is perplexing;
occurred between formation of the Mo ore shells of the Ny- perhaps the initial composition of these fluids was less acidic
strom and Vasquez stocks (initial deposition of the TPZ-PY than the Henderson and Seriate fluids, permitting the
assemblage). Similarly, juvenile fluids also were not entering Vasquez fluids to miss the sericite and/or muscovite field
when the large shift in Zn/Mn ratios of veins occurred dur- upon cooling. An analogous situation has been observed at
ing the onset of deposition of the RHOD assemblage (Fig. the Buffalo Valley deposit, a porphyry copper system with late
16). veins that was mined for gold. There, late dikes that contain
Our suggestion that metals deposited at moderate to low secondary biotite (though barren of copper) are cut by gold-
temperatures (W, Pb, Zn, and Mn at Henderson but includ- bearing pyrite veins that lack alteration envelopes (Seedorff
ing Mo in many porphyry copper systems) are introduced at et al., 1991), which would be roughly comparable to a hypo-
high temperatures with the metals that are deposited at high thetical sequence at Henderson of a fluid skipping directly
temperatures (Mo at Henderson, but Cu ± Au in porphyry from the QTZ-KSP-MO to the SPHAL assemblage.
copper deposits) is consistent with microanalysis of fluid in- Hence, changes in initial composition of fluids over time at
clusions from porphyry deposits. For example, high-tempera- Henderson probably are slight and occur on time scales com-
ture fluid inclusions associated with ore at Bingham, Butte, parable to the emplacement of several intrusive centers. If
Grasberg, and Bajo de la Alumbrera have Pb, Zn, and Mn the Henderson interpretation were applied to other por-
concentrations that are as much as an order of magnitude phyry districts, such as Yerington (Dilles, 1987; Dilles and
higher than the concentrations of Cu (Anderson et al., 1989; Proffett, 1995; Dilles et al., 2000b), the analogy would be
Bodnar, 1995; Heinrich et al., 1999; Ulrich et al., 1999, 2001), that changes in the composition of fluids derived from a large
even though Pb, Zn, and Mn minerals are not reported in evolving magma chamber may account for differences be-
more than trace amounts in the associated high-temperature tween intrusive centers, such as differences in metal content
mineral assemblages. Virtually all metals ultimately deposited between the Yerington deposit (mineralized with Cu but vir-
in the system probably were present in the high-temperature tually free of Mo) and the Ann-Mason deposit (a Cu-(Mo)
fluids. deposit).
Although it is tempting to assume that components de-
posited at lower temperature (or later) were introduced later Mode of release of magmatic
than components deposited at higher temperature (or ear- hydrothermal fluids between intrusive centers
lier), we attribute changes in metal ratios in successive vein The majority of juvenile, Cl-rich hydrothermal fluid re-
sets at Henderson to thermal and compositional evolution of leased from the apices of intrusions at Henderson generally
previously introduced magmatic fluids (see below) and sug- escaped upward, marked by high-temperature, steep, gener-
gest that other porphyry-related systems may have behaved ally thin, radial replacement veinlets (Carten et al., 1988a, b).
similarly. We conclude that these same fluids (samples of which are
trapped in high-temperature fluid inclusions; Carten, 1987)
Change in composition of evolved to form the suite of lower temperature assemblages
juvenile magmatic fluid evolved over time above intrusive centers. Fluid inclusion results (Table 1) indi-
Only slight variations are observed in the sequences and cate that the fluids remained highly saline from potassic
abundances of lower temperature assemblages formed above through intermediate argillic alteration.
the Henderson and Seriate centers. For example, brown bi- In contrast, a significant fraction of the fluid released from
otite is more abundant in the QTZ-KSP-MO and MT-KSP as- the apex of the Seriate stock was injected downward and out-
semblages around the Seriate center than around the Hen- ward from the apex, because of the bulletlike geometry of the
derson center, and hydrothermal garnet is present in a stock and fluid pressures in excess of lithostatic (Carten et al.,
distinct, low-temperature garnet-rich assemblage (GAR) 1988a, b). This mode of fluid release is marked by high-tem-
above the Henderson center but is a minor component of perature, gently outward dipping concentric, open-space and
many moderately high to low-temperature assemblages replacement veins, with the open-space veins tending to be
around the Seriate center (Fig. 2; Seedorff and Einaudi, wide. Fluids that were injected downward and outward
2004). The similarity in assemblages developed around the evolved to form the distinctive suite of lower temperature as-
two centers suggests minimal change in the initial composi- semblages on the flanks of the Seriate center (Figs. 2–3, 16).
tions of juvenile hydrothermal fluids introduced by stocks of The suite is characterized by less-saline fluid inclusions (Fig.
the Henderson versus the Seriate center. 7, Table 1), produces contrasting mass transfer effects (Fig.
The initial compositions of fluids ultimately may have 11), and defines an evolutionary path at different sulfidation
changed upon initiation of the Vasquez center, because mod- and oxidation states and cation activity ratios than fluids above
erately high and moderate-temperature assemblages and W intrusive centers (Fig. 14). Fluids on the flanks of the Seriate
mineralization are nearly absent above the Vasquez center, center could represent evolved versions of the low Cl, F-rich,
and low-temperature assemblages occur in distinctly lower Fe- and K-bearing aluminosilicate fluid inclusion population

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observed in high-temperature veins (Carten, 1987; R. B. positions of Mo versus W and of Mo versus Cu at the
Carten, pers. commun., 1987). Turquoise Gulch porphyry copper deposit at El Salvador
The Henderson case suggests that the mode of accumula- (Gustafson and Quiroga G., 1995, p. 12) are both reversed
tion and release of magmatic hydrothermal fluids from the from those documented at Henderson. We suggest that, in
apices of mineralizing intrusions influences their subsequent spite of these variations, the operative processes of metal in-
evolution and is a source of diversity of hydrothermal mineral troduction and deposition may be similar among porphyry-re-
assemblages. Other porphyry deposits that have both high- lated deposits.
angle radial and low-angle, outward-dipping, high-tempera- The Henderson case emphasizes the distinction between
ture veins might also display contrasting paths of fluid evolu- the processes of introduction and deposition of components
tion related to different vein sets. during primary dispersion (see also Hemley and Hunt, 1992,
p. 40). Fluids evolve in the environment of deposition as they
Evolution of hydrothermal fluids, migrate—rising upward, collapsing downward, and flowing
deposition of components at moderate and inward or outward—by reacting with wall rocks, boiling, mix-
low temperatures, and origin of metal zonation ing with other fluids, and cooling. A variety of processes are
Porphyry deposits typically involve a series of porphyry in- potentially involved, but some degree of spatial (and tempo-
trusions and a complex sequence of hydrothermal mineral as- ral) separation between the site (and time) of introduction of
semblages and associated metals. At Henderson, there were components and the eventual deposition of various metals is
numerous periods of Mo deposition at high temperatures expected as fluids evolve. The separation results from differ-
during intense potassic alteration in multiple ore shells re- ent initial concentrations of the various metals, solubilities of
lated to separate stocks, one significant W depositional event metals, water/rock ratios, and solubility responses to changes
at moderate temperatures primarily in a topaz-bearing in temperature, pressure, and composition of fluids (Hemley
sericitic assemblage in two zones above the Henderson and et al., 1967, 1986, 1992; Barnes, 1975, 1979; Hemley and
Seriate centers, and one Pb-Zn and Mn depositional event at Hunt, 1992; Reed, 1997). As a result, the youngest intrusion
low temperatures during intermediate argillic and carbonate cut by a given mineral assemblage is not necessarily the only,
alteration above each of the three intrusive centers (Fig. 16). or even dominant, source of magmatic components deposited
Hence, the temporal sequence of metal deposition with de- in that assemblage, as at Henderson. The same may be true
crease in temperature at Henderson is Mo, followed by W, at other porphyry deposits where metals deposited at low
then Pb + Zn ± (Cu), and finally Mn (Figs. 15–16). The spa- temperature (and late) commonly have been interpreted as
tial arrangement of metals from proximal to distal depends in having been introduced at the time of late intrusions (e.g.,
part on the flow directions of fluids over time, but the zona- Late Barren stage at Climax, Wallace et al., 1968; late Sn-Pb-
tion patterns commonly, but not in every case (exceptions are Zn-Cu mineralization at Mt. Pleasant, Kooiman et al., 1986;
where arrows turn downward in Fig. 15H), mimic the tem- relatively late Mo at Bingham, Redmond et al., 2001). De-
poral sequence of deposition, i.e., proximal Mo, followed by coupling of the introduction and the deposition of compo-
W, then Pb + Zn ± (Cu), and distal Mn. nents deposited at low temperatures, such as Pb, Zn, Mn, Ag,
The deposition of Pb and Zn at low temperatures at Hen- and Au, may be most pronounced in porphyry districts that
derson is particularly instructive. Pb and Zn were deposited have well developed distal halos of these metals, such as Bing-
principally in the SPHAL assemblage in essentially a single ham (Babcock et al., 1995), Butte (Meyer et al., 1968), and
event at low temperatures but in three separate spatial zones Yauricocha (Petersen, 1965; Alvarez and Noble, 1988).
(Figs. 15F, 16). Each Pb-Zn zone can be readily related to the
migration of fluids from each of the three intrusive centers Degree of decoupling of introduction and
(Fig. 15I); Pb and Zn remained in solution during protracted deposition of metals as a geochemical
evolution of these fluids, while higher temperature assem- classification tool in porphyry deposits
blages developed, until the temperature declined to 380 to The evidence that the majority of Mo at Henderson was de-
200ºC (Fig. 16, Table 1). Magmatic hydrothermal fluids re- posited at high temperatures is compelling: most molybden-
leased from the Seriate and Henderson stocks were the prin- ite is in veinlets with K-feldspar envelopes; veinlets exhibit a
cipal sources of Pb-Zn, even though all Pb-Zn zones formed strong spatial and temporal relationship to crystallization of
after emplacement of the younger stocks of the Vasquez cen- individual mineralizing stocks; and Mo-grade contours are
ter. As suggested by Wallace et al. (1978, p. 347–348) and M. closely spaced and geometrically related to apices of stocks
D. Barton (pers. commun., 2001), cooling of the principal (Carten et al., 1988b; Seedorff and Einaudi, 2004, figs. 2–3).
host rock (Urad porphyry), rather than cooling of the later, This relationship seems to hold for other Climax-type de-
but smaller, mineralizing stocks, may have controlled deposi- posits.
tion of low-temperature mineral assemblages and metals. Mineral assemblages, crosscutting relationships, and grade
The sequences and patterns of metal deposition differ only distributions are less well documented in most porphyry cop-
slightly between different intrusive centers at Henderson per deposits, but the deposition of Cu tends to be less re-
(Fig. 15). Although there is variation, the sequences and pat- stricted to a single assemblage or vein type. The relative tim-
terns of metal deposition tend to be similar between deposits ing and temperature of Cu deposition in most porphyry
of the same type (e.g., between Climax-type porphyry molyb- copper deposits is controversial. One view (Fig. 18A) holds
denum deposits). Greater differences in the sequence and/or that most of the Cu is deposited relatively early, at relatively
pattern of metal deposition are observed between different high temperatures (commonly >400ºC) as chalcopyrite ±
types of porphyry deposits. For example, the relative spatial (bornite + digenite) ± magnetite synchronous with potassic

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A. Cu deposited at high temperatures B. Cu deposited at moderately high C. Cu deposited at moderate

as chalcopyrite ± (bornite + digenite) temperatures as chalcopyrite ± temperatures as chalcopyrite ±
± magnetite synchronous with pyrite synchronous with pyrite synchronous with
potassic alteration transitional stage alteration chlorite ± sericite alteration

Pre-Ore Intrusive Center Pre-Ore Intrusive Center Pre-Ore Intrusive Center

Tree Diagrams

Early Mineralizing Center Early Mineralizing Center Early Mineralizing Center

Evolutionary

Intermediate Center Intermediate Center Intermediate Center

Late Barren Center Late Barren Center Late Barren Center
Intense Potassic (± Silicic) Intense Potassic (± Silicic) Intense Potassic (± Silicic)

Cu Potassic Potassic Potassic

TEMPERATURE

TEMPERATURE

TEMPERATURE
Transitional Cu Transitional Transitional

Sericitic Sericitic Cu Sericitic

Intermediate Intermediate Intermediate
Argillic Argillic Argillic

Carbonate Carbonate Carbonate

FLUID EVOLUTION (~TIME) FLUID EVOLUTION (~TIME) FLUID EVOLUTION (~TIME)

Intermediate Transitional Intermediate Transitional Intermediate

Transitional
Argillic Argillic Argillic
Space -Time

Potassic Sericitic
Sericitic
Cu
SPACE (elevation)

SPACE (elevation)

SPACE (elevation)
Diagrams

Cu
Potassic Potassic Sericitic
Cu

Intense Carbonate Intense Carbonate Intense Carbonate

Potassic Potassic Potassic
(± Silicic) (± Silicic) (± Silicic)

early TIME late early TIME late early TIME late

Increasing Decoupling of Introduction and Deposition of Cu

FIG. 18. Simplified set of evolutionary tree diagrams and space-time diagrams, illustrating varying degrees of decoupling
between introduction and deposition of copper in three different types of porphyry deposits. A. Copper deposited primarily
in potassic types of assemblages at high temperatures. This case may apply to deposits such as Bingham, El Salvador, Yer-
ington, Dos Pobres, Lakeshore, and Bajo de la Alumbrera. B. Cu deposited primarily in Transitional-stage assemblages at
moderately high temperatures. This case may apply to Toquepala. C. Cu deposited primarily in sericitic-type assemblages at
moderate temperatures. This case may apply to Sierrita-Esperanza, Santa Rita, Ann-Mason, and Far Southeast.

alteration (e.g., Hemley and Hunt, 1992; Gustafson et al., Toquepala, where the highest Cu and Mo grades are in Tran-
1999; Dilles et al., 2000a), resulting in the orebody being sitional veins (in the sense of Gustafson and Hunt, 1975) that
largely within the zone of potassically altered rocks. This view predate inception of sericitic alteration but postdate both
is supported by studies of deposits such as Bingham (Atkin- potassic alteration and tourmaline breccia formation (Zweng
son and Einaudi, 1978; Phillips et al., 1997; Redmond and and Clark, 1995). Rarely, ore-grade Cu is deposited through-
Einaudi, 2000), El Salvador (Gustafson and Hunt, 1975; out the entire range of potassic, sericitic, and advanced
Gustafson and Quiroga G., 1995), Yerington (Proffett, 1979; argillic alteration, as at Superior (Manske and Paul, 2002).
Carten, 1986; Dilles et al., 2000b), Dos Pobres (Langton and Each view may be correct at the deposits in question. If Cu
Williams, 1982), Lakeshore (Huyck, 1990), and Bajo de la is of magmatic origin and all three views are correct in at least
Alumbrera (Proffett, 1999; Ulrich and Heinrich, 2001). A sec- some deposits (Fig. 18), then we suggest that differing initial
ond view (Fig. 18C) holds that potassic alteration is largely compositions of fluids and contrasting evolutionary paths be-
barren and that most of the Cu is deposited much later, at tween deposits may produce differing relative amounts of
moderate temperatures (commonly 350º–250ºC) with pyritic, separation in space and time between introduction and depo-
biotite-destructive, chlorite ± sericite-stable mineral assem- sition of a single component (Cu), just as evolution of hy-
blages that are broadly synchronous with onset of sericitic al- drothermal fluids with decline in temperature produces sep-
teration, resulting in the orebody straddling the deposit-scale aration in space and time of different metals in a given
interface of potassic and sericitic alteration (e.g., Crerar and deposit such as Henderson. As a first step, the degree of de-
Barnes, 1976; Barnes, 1979; Beane and Titley, 1981; Beane, coupling between introduction and deposition of Cu might be
1983; Hedenquist et al., 1998). This view is consistent with used as a geochemical classification tool for well-studied de-
descriptions of Sierrita-Esperanza (Preece and Beane, 1982; posits. The observational underpinnings of past attempts to
West and Aiken, 1982), Santa Rita (Reynolds and Beane, model deposit-scale zoning (e.g., Barnes, 1975) understate
1985), Ann-Mason (Dilles and Einaudi, 1992), and Far South- the diversity of deposition of metals in porphyry deposits
east (Hedenquist et al., 1998). Among many other variations (Fig. 19). Hence, the abundance, timing of deposition, and
on this theme is a third scenario (Fig. 18B) documented at spatial distributions of Mo and Au relative to Cu in various

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 65

TYPES OF
Mo Cu ASSEMBLAGES

Carbonate

LOW
Intermediate Argillic

Temperature
(± Advanced Argillic)

rson Sericitic

MOD.
Hende
El Salvado Transitional
r
Superior
MOD.
HIGH

Potassic
Hall
HIGH

Intense Potassic
(± Silicic)
Henderson

Low Cu/Mo High

FIG. 19. Instantaneous Cu/Mo metal ratios as a function of fluid evolution for selected porphyry-related deposits. Ap-
proximate metal ratios are deduced from mineralogy of successive hydrothermal mineral assemblages for the Henderson
porphyry Mo deposit (this study), the Hall (Nevada Moly) porphyry Mo-Cu deposit (Shaver, 1991), and the Resolution
(Magma Porphyry) deposit in the Superior district (Manske and Paul, 1998) and El Salvador (Gustafson and Hunt, 1975)
porphyry Cu-(Mo) deposits. Alteration type (right side) and temperature of formation (left side) are used to monitor fluid
evolution. The bottom of the diagram generally corresponds to deep and early products and the top to shallow and late prod-
ucts. The variation in width along a path schematically indicates the relative mass of metal (Cu or Mo) deposited instanta-
neously. The path is discontinuous if there are periods when neither Cu nor Mo was deposited; the gaps are traversed by dot-
ted lines that connect discontinuous segments of the path.

deposits could be incorporated in a systematic investigation of the flanks of the Seriate center (Table 2). Those deposits con-
depositional controls for metals in porphyry-related deposits. tain abundant biotite, in part coexisting with topaz, but the as-
sociated fluids had even lower oxidation and sulfidation states
Deposition of topaz, geochemical paths, and similarities of than fluids on the flanks of the Seriate center. Most of the
alteration-mineralization with other deposits above deposits are granite-related Mo deposits of the high-sil-
Nowhere at Henderson is topaz present in high-tempera- ica rhyolite-alkalic suite of Carten et al. (1993).
ture assemblages of the silicic and intense potassic types, Carten at al. (1993) also defined two other types of por-
which contain the vast majority of molybdenite. Saturation phyry molybdenum deposits, granite-related Mo deposits of
with respect to topaz occurred subsequently upon decrease in the differentiated monzogranite suite (e.g., Quartz Hill, En-
temperature and may have been promoted by a decrease in dako, Cannivan Gulch, and East Kounrad) and granite-re-
pressure. In both suites of assemblages, the evolutionary lated Mo-Cu deposits (e.g., Mount Tolman, Hall, Bucking-
paths of fluids eventually passed again into the topaz-absent ham, El Crestón (Opodepe), Cumobabi, and Mocoa). These
field during sericitic and intermediate argillic alteration. two types of porphyry molybdenum deposits generally lack
In the suite of assemblages that formed above intrusive hydrothermal topaz. Although a few of those deposits contain
centers at Henderson, topaz was deposited almost exclusively fluorine anomalies and accessory fluorite (e.g., Hall: Shaver,
in a single, sericitic-type assemblage. This suite is similar to 1986, 1991), most tend to be fluorine poor (Theodore and
alteration-mineralization assemblages of many porphyry Menzie, 1984; Carten et al., 1993). Their alteration-mineral-
molybdenum deposits associated with high-silica rhyolites, in- ization products do no have much in common with either
cluding Urad, Climax, and Questa (Table 2), although the key suite of assemblages at Henderson and have greater similar-
minerals magnetite, topaz, and fluorite are not all reported ity to alteration-mineralization in porphyry copper deposits or
from each deposit. tin-tungsten vein and greisen deposits.
In the suite of assemblages formed on the flanks of the Se- The similarities and contrasts between deposits and in dif-
riate center, topaz was deposited in a variety of assemblages, ferent parts of the Henderson deposit underscore the impor-
which are of potassic, sericitic, transitional potassic-sodic, and tance of defining the geochemical environment of wall-rock
transitional sericitic-sodic types. Relative to the other suite, alteration and ore deposition on the basis of mineral assem-
fluids that formed this suite evolved along a path of lower ox- blages as a step toward systematization and classification of
idation and sulfidation states, slightly higher aK+/aH+ and mineral deposits.
higher aNa+/aK+. Alteration-mineralization at the porphyry
molybdenum deposit associated with an alkali granite-syenite Conclusions
complex at Malmbjerg and the porphyry tungsten-molybde- 1. A geologic evaluation of the fluid inclusion results
num deposits associated with rhyolites and granites at Mount suggests that we failed to gather data for several of the
Pleasant and True Hill are similar to the suite that formed on hydrothermal mineral assemblages that were targeted (i.e.,

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TABLE 2. Alteration-Mineralization Suites at Henderson Compared to Other Deposits

Suite of hydrothermal mineral

assemblages at Henderson Deposits with similar assemblages References

Above intrusive centers

Bear Mountain, Alaska Barker and Swainbank (1986)
Climax, Colorado Steininger (1973)
Jinduicheng, Shaanxi Province, China Stein et al. (1997)
Mount Emmons-Redwell Basin, Colorado Sharp (1978); Dowsett et al. (1981);
Thomas and Galey (1982)
Mount Hope, Nevada Westra and Riedell (1996)
Pine Grove, Utah Phelps Dodge Corporation staff and
Pine Grove Joint Venture staff (1984);
Keith et al. (1986); Keith and Shanks (1988)
Questa, New Mexico Leonardson et al. (1983); Molling (1989)
Urad, Colorado MacKenzie (1970); Wallace et al. (1978)

Flanks of Seriate center

Malmbjerg, Werner Bjerge alkaline complex, Bearth (1959); Harpøth et al. (1986)
East Greenland
Mount Pleasant, New Brunswick, Canada Dagger (1972); Kooiman et al. (1986); Samson (1990)
True Hill, New Brunswick, Canada Lentz et al. (1988); Lentz and McAllister (1990)

inclusions measured were unrelated, secondary inclusions). along gently outward-dipping, concentric veins. These fluids
The moderately high temperature group of assemblages evolved to form a distinctive suite of lower temperature as-
probably formed at 600° to 460°C, the moderate-tempera- semblages on the flanks of the Seriate center.
ture assemblages at 530° to 310°C, the low-temperature as- 8. Metals deposited at moderate to low temperatures (W,
semblages at 390° to 200°C, and propylitic alteration at 320° Pb-Zn, and Mn) were introduced synchronous with Mo at
to 210°C. The fluid inclusions from the suite of assemblages high temperatures but were not deposited until fluids evolved
formed on the flanks of the Seriate center generally are not to lower temperatures. The delayed deposition of some met-
halite saturated, whereas many of the inclusions related to as- als relative to others, coupled with flow of fluids, led to a spa-
semblages formed above intrusive centers commonly contain tial zonation. There was progressively greater decoupling be-
halite (± sylvite). High salinities persisted through sericitic tween the times of introduction and deposition of metals
and intermediate argillic alteration, indicating lack of signifi- from those deposited at high temperatures (e.g., Mo) to those
cant dilution by meteoric waters during this portion of the deposited at low temperatures (e.g., Mn). This time delay
evolution of hydrothermal fluids. lengthened for metals introduced by an earlier intrusion com-
2. Phase equilibria indicates that fluids followed essentially pared to the same metal introduced by a later intrusion. The
constant aK+/aH+ during the transition from potassic to degree of decoupling of introduction and deposition of met-
sericitic alteration, such that the transition was promoted by a als may be useful as a classification tool in porphyry copper
decline in temperature, consistent with the fluid inclusion re- deposits.
sults.
3. Fluorine was continuously added to wall rocks along the Acknowledgments
entire evolutionary paths of both suites of assemblages. The Exploration, development, and mine geologists at the Urad
alkalis underwent a complex history of mass transfer, with the and Henderson mines made this study possible; Will White,
behavior of potassium fluctuating between periods of strong Rick Carten, Bob Kamilli, and Bruce MacKenzie deserve
leaching and strong addition to the rock. Iron was leached at special note in the context of this paper. Judy Hannah, Jeff
high to moderately high temperatures and then fixed in the Keith, Mark Hannington, Carten, Gail Mahood, George
rock at lower temperatures. Parks, Mark Barton, Dave John, Mark Sander, Paul Zweng,
4. There is no evidence of deposit-scale leaching or redis- and Holly Stein read various sections and versions of the
tribution of Mo or W during evolution of the hydrothermal manuscript and catalyzed its improvement. The phase equi-
system. libria involving topaz was made possible by Barton’s experi-
5. Integration of space-time relationships indicates that mental work, and he helped make the thermodynamic data
metal-bearing volatiles could have been fluxed into the envi- set used in this work internally consistent. This study bene-
ronment of deposition only during the crystallization of the fited from the assistance of Dennis Bird, Don Burt, Mike
tops of mineralizing intrusions. Gutierrez, Ken Jackson, and Perfecto Mari and discussions
6. Compositions of juvenile hydrothermal fluids were sim- with Frank Mazdab. We extend special thanks to Carten,
ilar between successive mineralizing stocks through stocks of John, Barton, John Dilles, Lew Gustafson, John Proffett, Jeff
the Henderson and Seriate intrusive centers but may have Keith, and Steve Shaver for their decades of contribution to
changed upon initiation of the Vasquez center. our inquiry into the origin of porphyry deposits. Seedorff ac-
7. A significant fraction of the fluid released from the Seri- knowledges Rick Carten’s unwavering professional support,
ate stock was injected downward and outward from the apex mentoring, and generosity.

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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 67

This project was supported financially by National Science Bright, M.J., 1974, Primary geochemical dispersion associated with the
Foundation grant EAR-85-07264 (to MTE); Climax Molyb- Henderson molybdenum deposit [abs.]: ECONOMIC GEOLOGY, v. 69, p.
1177.
denum Company, Western Operations, Golden, Colorado, Brimhall, G.H, Jr., 1979, Lithologic determination of mass transfer mecha-
while headed by Will White, Chief Geologist; Chevron Fel- nism of multiple stage porphyry copper mineralization at Butte, Montana:
lowship, ASARCO research grant, and Mudd Fund in the Vein formation by hypogene leaching and enrichment of potassium-silicate
Department of Applied Earth Sciences; and a travel grant protore: ECONOMIC GEOLOGY, v. 74, p. 556–589.
——1980, Deep hypogene oxidation of porphyry copper potassium-silicate
from the Shell Companies Foundation to the School of Earth protore at Butte, Montana: A theoretical evaluation of the copper remobi-
Sciences, Stanford University. lization hypothesis: ECONOMIC GEOLOGY, v. 75, p. 384–409.
——1999, Main stage Butte vein formation by hypogene leaching of pre-
January 11, 2002; July 16, 2003 Main Stage mineralization under oxidizing and sulfidizing conditions [abs.]:
Geological Society of America Abstracts with Programs, v. 31, no. 7, p.
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oxygen and halogen fugacities in the CanTung and other W-related grani- British Columbia: ECONOMIC GEOLOGY, v. 75, p. 45–61.
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Wallace, S.R., 1974, The Henderson ore body—elements of discovery, re- v. 90, p. 1329–1337.
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Wallace, S.R., Muncaster, N.K., Jonson, D.C., MacKenzie, W.B., Bookstrom, Geochimica et Cosmochimica Acta, v. 53, p. 303–312.
A.A., and Surface, V.E., 1968, Multiple intrusion and mineralization at Cli- Wood, S.A., Crerar, D.A., and Borcsik, M.P., 1987, Solubility of the assem-
max, Colorado, in Ridge, J.D., ed., Ore deposits of the United States, blage pyrite-pyrrhotite-magnetite-sphalerite-galena-gold-stibnite-bis-
1933–1967 (Graton-Sales Volume): New York, American Institute Mining muthinite-argentite-molybdenite in H2O-NaCl-CO2 solutions from 200° to
Metallurgy and Petroleum Engineers, v. 1, p. 605–640. 350°C: ECONOMIC GEOLOGY, v. 82, p. 1864–1887.
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ology of the Urad and Henderson molybdenite deposits, Clear Creek drogen isotope geochemistry of pre-Main Stage porphyry Cu-Mo mineral-
County, Colorado, with a section on a comparison of these deposits with ization at Butte, Montana [abs.]: Geological Society of America Abstracts
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 HENDERSON PORPHYRY Mo II: EVOLVING FLUIDS 71

APPENDIX
Fluid Inclusion Studies
Sample selection upon heating, are shown at the bottom of Figure 7. The
Samples for fluid inclusion investigation were sought that shapes of fluid inclusions range from irregular to negative
represented a minimum number of geologic events. Detailed crystal forms (the latter are common); the usual precautions
petrography was conducted on 36 doubly polished wafers of were taken to avoid fluid inclusions that may have necked off.
the most promising samples. Microthermometric measure- For the 300 fluid inclusions for which microthermometric
ments were conducted on 14 wafers, the locations of which are data were obtained, the range in sizes (max dimension; 1-µm-
shown in Figure A1, resulting in data on 300 fluid inclusions. size intervals) is 4 to 29 µm, the mean is 9.5 µm, the median
is 8 µm, and the mode is 6 µm.
Methodology The criteria of Roedder (1984, p. 43–45) were used as a
guide to classify the origin of fluid inclusions as primary, pseu-
Microthermometric studies of fluid inclusions were per- dosecondary, or secondary, except that large size and negative
formed on a Fluid Inc. modified version of the USGS gas-flow crystal shape were not used as criteria for primary fluid inclu-
heating/freezing system calibrated with synthetic fluid inclu- sions because these attributes characterized many inclusions
sions and operated using standard techniques (Roedder, 1984, that clearly are of secondary origin. The material available in
p. 196–201). The combined errors of thermocouples, temper- this study, however, precludes objective assignment of many
ature indicators, and thermal gradients in the sample chamber fluid inclusions to any category with confidence, in part be-
limit the estimated accuracy of homogenization temperatures cause of the absence of growth zoned minerals in the veinlets
to ±2° at 200°C to approximately ±10° at 600°C (e.g., Pasteris, of interest and because of the high abundance of (mostly
1983; Smith, 1983; Bodnar et al., 1985, p. 1864). Uncertainties small) fluid inclusions. Although all of the fluid inclusions
in laboratory measurements used to calculate salinity from salt hosted by quartz phenocrysts probably are of secondary
daughter mineral dissolution and freezing temperatures prob- origin, fluid inclusions were termed secondary only if they
ably are a few percent. The conversion of those data to salini- could be assigned to a planar array with the characteristics
ties using model chemical systems typically introduces consid- noted by Roedder (1984). For many fluid inclusions, includ-
erable uncertainty, although it is minimal for Henderson ing those hosted by vein-filling minerals, it is difficult to de-
because of its association with magmas and wall rocks of sili- cide to which plane, if any, a given inclusion belongs. Because
cic, mafic-poor compositions and with low CO2 magmas. As the fluid inclusions are neither clearly of secondary origin nor
discussed in the text, uncertainties in geologic interpretation meet Roedder’s (1984) criteria for primary or pseudosec-
exceed the analytical and geochemical uncertainties for both ondary origins, all remaining fluid inclusions (of ambiguous
temperature and salinity. Samples are described in greater de- origin) are termed secondary(?) fluid inclusions.
tail in Seedorff (1987, app. B). Documentation of each run
and additional information on fluid inclusion procedures are Characteristics
contained in Seedorff (1987, app. C). Liquid-rich fluid inclusions are common, but many fluid
inclusions contain daughter salts that indicate that the fluids
Classification were brines. Vapor-rich fluid inclusions were observed in one
The various types of fluid inclusions that were observed, sample, which also contains the only fluid inclusion that ap-
based on the identity of contained phases and their behavior peared to homogenize by critical behavior.

WEST 52N-N63E-58N Section EAST NORTHWEST 480 H Section SOUTHEAST

Elev., Ft Elev., Ft
CX-163-499 FLUID INCLUSION
10,000 10,000 CX-158-445 RHOD
CX-163-499 PROPYLITIC SAMPLE SITES
RHOD CX-91-1059
GAR Drill hole trace
FLUID INCLUSION
SAMPLE SITES CX-93-814 Sample
n CX-93-814
n tai SPHAL Drill hole trace tain SPHAL Target Assemblage(s)
ou un
dM Mo
Re Sample Red Site projected into section
CX-158-1416
Target Assemblage(s) SER-PY H-268-380 Sample
MT-KSP Target Assemblage(s)

H-074-24 H-321-314
TPZ-PY, SER-PY MOTTLED KSP-QTZ
CX-98-2908
TPZ-MT, SER-MT
H-430-452.5 H-323-842
BIO-KSP H-499-295.2
BIO-KSP H-471-255 TPZ-PY, GREEN BIO
H-488-713.9 BIO-KSP TPZ-PY, GREEN BIO
7,000 7,000
0 METERS 500 0 METERS 500
480H N63E
50E BEND 60E BEND 70E A 50E 60E 70E B

FIG. A1. Location of samples for which fluid inclusion heating experiments were conducted, displayed on sections 52N-
N63E-58N and 480-H, labeled with target assemblages.

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 72 SEEDORFF AND EINAUDI

The salt-bearing fluid inclusions contain halite, and several H2O-NaCl-KCl system, fluids could contain as much as 11
also contain sylvite. Most halite-bearing fluid inclusions ho- percent KCl (depending on NaCl content and homogeniza-
mogenized by vapor disappearance after halite dissolution tion temperature) without being saturated with respect to
(bottom of Fig. 7). Hematite (which did not dissolve upon sylvite at room temperature. Hence, the salinity expressed as
heating) is common, particularly in halite-bearing inclusions. wt percent NaCl + KCl equiv could be several percent higher
A rhombohedral, highly birefringent daughter mineral that than the estimates reported as wt percent NaCl equiv. For the
dissolved prior to vapor disappearance, presumably a carbon- few successful freezing runs (not available for samples shown
ate, is present is some of the fluid inclusions in the sample in in Fig. 8), salinities are calculated in terms of wt percent NaCl
which RHOD is the targeted assemblage. Several unidenti- equiv (Potter et al., 1978).
fied daughter minerals were observed (Seedorff, 1987, app. Considering that iron-bearing hydrothermal phases are
C), including a small cubic phase that did not dissolve upon present at Henderson (Fig. 2), FeCl2 is almost certainly pre-
heating (fluorite?) and at least two opaque phases, one of sent in the fluids, thereby reducing solubilities of NaCl and
which (e.g., in samples where BIO-KSP is the target assem- KCl by the salting out effect and resulting in overestimation
blage) could be molybdenite (see Kamilli, 1978; White et al., of Na and K abundances based on microthermometry (Cline
1981, p. 299). and Vanko, 1995, p. 167). The actual FeCl2 contents of Hen-
derson fluids have not been determined but are expected to
Model geochemical systems be lower than those at the Granisle porphyry copper (Quan et
Fluids from the Henderson deposit should be the best nat- al., 1987) and Questa porphyry molybdenum (Cline and Bod-
ural analogue of the system H2O-NaCl-KCl, given that both nar, 1994; Cline and Vanko, 1995) deposits because the stocks
wall rocks and mineralizing intrusions are high-silica rhyolites and wall rocks at Henderson are Fe poor.
that are poor in Ca, Mg, and Fe, although other components Henderson fluids are considered to have been relatively
must be present in minor amounts. Phase equilibria of this poor in CO2, particularly relative to fluids associated with flu-
system (Roedder, 1984, p. 245) indicate that an inclusion the- orine-poor porphyry molybdenum deposits (Theodore and
oretically could have a salinity exceeding 29 wt percent NaCl Menzie, 1984; Theodore et al., 1992), so the effect of CO2 on
+ KCl without precipitating either halite or sylvite daughters phase equilibria is assumed to be minimal. Nonetheless, a fi-
at room temperatures; salinities, therefore, are reported in nite amount of CO2 must have been present, at least in the
Figures 7 and 8 as <29 wt percent equiv if freezing data are low-temperature fluids, for rhodochrosite to have been de-
not available and neither halite nor sylvite were observed. posited. Liquid CO2 was not observed in this study, although
Salinities are reported in terms of wt percent NaCl + KCl R. J. Kamilli (oral commun., 1986) and R. B. Carten (oral
equiv. (Roedder, 1984, p. 245) if both halite and sylvite were commun., 1987) have observed rare fluid inclusions from
present, but in terms of wt percent NaCl equiv if only halite Henderson with liquid CO2.
was present at room temperature (Potter et al., 1977). In the

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