©2018 Society of Economic Geologists, Inc.

Economic Geology, v. 113, no. 6, pp. 1269–1295

White Mica Geochemistry of the Copper Cliff Porphyry Cu Deposit:

Insights from a Vectoring Tool Applied to Exploration
Camilo Uribe-Mogollon† and Kierran Maher
The New Mexico Institute of Mining and Technology, Socorro, New Mexico 87801, USA

Abstract
The Copper Cliff porphyry copper prospect, located 48 km east-southeast from Missoula, Montana, presents
two distinct phyllic alteration events: an early green-colored expression, locally texturally destructive and associ-
ated with specular hematite and hypogene copper mineralization, and a later white variety generally structurally
controlled and associated with pyrite. Variations in the mineral chemistry of white micas were evaluated by
short-wave infrared spectroscopy, electron microprobe analysis, and laser ablation-inductively coupled plasma-
mass spectrometry (LA-ICP-MS). The analytical results allow the identification of a systematic compositional
variation of the white micas, possibly controlled by redox changes in the system. The early green phyllic expres-
sion consists of Fe-bearing white micas characterized by longer Al-OH absorption wavelength (2,206–2,210 nm)
and formed by oxidized magmatic fluids, whereas the late white phyllic phase contains white micas enriched in
V and Sc with shorter Al-OH absorption wavelengths (2,197–2,206 nm) formed under less oxidizing conditions.
Based on LA-ICP-MS trace element analyses of white micas, Cu concentrations decrease exponentially with
distance from the porphyry center, in contrast to Zn, which tends to increase. The application of the Cu/Zn ratio
of white micas in a manner analogous to the chlorite proximitor equation of Wilkinson et al. (2015) allows the
estimation to the center of the hydrothermal system within a radial distance of approximately 710 m in samples
of the early green phyllic alteration phase and within approximately 1,300 m in samples of the late white phyllic
alteration style. Therefore, the Cu/Zn ratio in white micas at Copper Cliff deposit may provide a useful tool for
targeting the hydrothermal center.

Introduction
As major ore deposit discoveries at the earth’s surface are
becoming increasingly uncommon, the development of geo-
chemical tools will become increasingly important to improve
the understanding of hydrothermal footprints and the effi-
cient identification of mineralization zones. Hydrothermal
footprints include a variety of mineralogical and geochemical
features related to the formation of ore deposits, with signa-
tures that indicate proximity to the center of the mineralized
system (Kelley et al., 2006). The variation of these signatures
is what can be referred to as geochemical vectors. Chemical
analyses in epidote and chlorite from propylitic halos around
porphyry copper systems suggest the existence of patterns
and/or trends in trace element concentrations that may indi-
cate proximity to hydrothermal centers (Cooke et al., 2014;
Wilkinson et al., 2015). In this study, we show that the compo-
sitional variations in major and trace element concentrations
in white mica from different phyllic alteration styles exist and
can be used to vector toward the center of the system. This
study focuses on the two white mica-bearing hydrothermal
alteration events at the Copper Cliff porphyry system: an early
and pervasive green to gray phyllic alteration typically associ-
ated with specular hematite and hypogene copper mineraliza-
tion and a late white phyllic alteration assemblage structurally
controlled and associated with pyrite.
Variations in major and trace element concentrations of
white micas, correlated with short-wave infrared signatures,
have indicated the potential for developing geochemical vec-
tors within phyllic alteration zones in porphyry copper sys-
tems (Alva Jimenez, 2011; Cohen, 2011); however, the vectors
have only been documented in white micas associated with
† Corresponding author: e-mail, camilo.uribe@student.nmt.edu
ISSN 0361-0128; doi: 10.5382/econgeo.2018.4591; 27 p.
Supplementary files available online. 1269
late quartz-sulfide veins, and it is not clear whether they per-
sist or are present in other phyllic events, such as early green
phyllic alteration documented in several porphyry hydrother-
mal systems (Sillitoe, 2010). For these reasons, the purpose of
this study is to describe the abundance and distribution of the
different phyllic alteration styles in the Copper Cliff system,
the compositional variations in major and trace elements, and
the infrared spectral absorption features to determine geo-
chemical changes at different distances from the porphyry
center that could be used as proximitors to the center of the
mineralized system.
The differentiation of multiple alteration events associated
with white mica represents a special challenge, principally due
to superposition of alteration or to enigmatic textural features
of the mineral assemblages, which are usually light colored,
fine grained, and difficult to distinguish with the naked eye
or hand lens. The Copper Cliff hydrothermal system clearly
shows two distinct phyllic alteration events, thereby provid-
ing an ideal setting for this study. Analytical techniques used
in this study include X-ray diffraction, 40Ar/39Ar geochronol-
ogy, short-wave infrared spectroscopy, electron microprobe
analyses, and laser ablation-inductively coupled plasma-mass
spectrometry. The results suggest that white mica geochem-
istry can be used to estimate distance from the Copper Cliff
orebody, and such knowledge may improve the efficiency of
the exploration program.
Phyllic Alteration
Phyllic alteration in porphyry Cu deposits is usually produced
by the hydrolytic reactions in which feldspar alters to white
micas at temperatures between 300° and 550°C (Seedorff
et al., 2005). At least two different subfacies are recognized
from a number of porphyry deposits and include an early
Submitted: December 22, 2017
Accepted: July 27, 2018

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 1270 URIBE-MOGOLLON AND MAHER
phase characterized by greenish to gray-color phyllosilicates
and a later phase characterized by white phyllosilicates (Sil-
litoe, 2010). The early phyllic alteration comprises the min-
eral assemblage of green mica and/or illite, quartz, iron oxides
(usually hematite), and locally chlorite, anhydrite, and/or
calcite. It has been reported in deposits such as Chuquica-
mata (northern Chile; Ossadón et al., 2001), Escondida Este
(northern Chile; Pizarro et al., 2015), and Taca Taca (north-
western Argentina; Sim et al., 2013) and from the authors’
personal experience in Resolution (Arizona, USA), the Cop-
per Cliff prospect (Montana, USA), and several other smaller
porphyry-related hydrothermal systems. It is usually observed
as pervasive, texturally destructive, proximally located mica-
ceous alteration locally with associated copper mineraliza-
tion comprising mainly chalcopyrite and bornite (Sillitoe,
2010). The late phyllic alteration is characterized by the min-
eral assemblage of white mica, quartz, and pyrite. It is more
commonly structurally controlled, forming halos of different
scales along fractures (Gustafson and Hunt, 1975). An exam-
ple of the most common expression of late phyllic alteration
includes D veins, which (per Gustafson and Hunt, 1975) are
quartz-sulfide veins with selvages of white mica and/or illites.
White mica compositions and spectral variations
White micas are considered the most characteristic alteration
mineral within phyllic alteration assemblages. Structurally,
they fall in the group of dioctahedral sheet silicates where each
O or OH ion is surrounded by two trivalent cations, commonly
Al3+. The simplified general formula is XY2Z4O10(OH,F)2,
where X includes large cations K+, Na+, Ca2+, Ba2+, Rb+, Cs+,
and Sr2+; Y represents octahedral coordinated cations such as
Al3+, Fe2+, Fe3+, Ti4+, Mg2+, Cr3+, Li+, Mn2+, V3+, and Ni2+; and
Z represents tetrahedral coordinated cations like Al3+ and Si4+
(Rieder et al., 1998; Deer et al., 2003).
In this work, the term “white mica” refers to minerals
constituting the phengite solid-solution series with composi-
tions varying between three end members: muscovite (K[Al2]
[AlSi3]O10[OH]2), Mg celadonite (K[Mg2][Si4]O10[OH]2), and
Fe celadonite (K[Fe2][Si4]O10[OH]2) (Rieder et al., 1998).
The muscovite-celadonite solid series can be explained by the
Tschermak coupled substitution where Fe2+ and Mg2+ sub-
stitutes for Al3+ in the octahedral site, with the substitution
of Si4+ in the tetrahedral site at an excess to what is typically
present in muscovite (Velde, 1965; Wang et al., 2017). Octahe-
dral site substitution requires the incorporation of silicon into
the tetrahedral site, producing white micas with transitional
compositions ranging from muscovite to celadonite, which are
normally referred to with the name “aluminoceladonite” (Rie-
der et al., 1998). Other important substitutions may occur in
the interlayer position, where Na+ or Ca2+ substitutes for K+,
forming paragonite (Na[Al2][AlSi3]O10[OH]2) and margarite
(Ca[Al2][Al2Si2]O10[OH]2), respectively; however, these are
not phengites (Rieder et al., 1998). White micas with inter-
layer cation deficiency (e.g., K + Na + Ca of 0.6–0.8 atoms
per formula unit) are referred to with the series name “illite”
(Bailey, 1984; Rieder et al., 1998). Illites are compositionally
similar in other ways to the white micas, therefore they are
included in this group for the purposes of this report.
The distribution and mode of occurrence of these substitu-
tions into the structural formula of phyllosilicates in porphyry
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systems has been proposed to be controlled by a number of
factors, including temperature, chemistry of the protoliths,
and the oxidation state and pH of the fluids (Shikazono and
Kawahata, 1987). Published compositional data of white mica
from the Ann-Mason porphyry Cu deposit in Nevada and the
Highland Valley porphyry Cu-Mo deposit in Canada show a
relationship with the increased content of sodium associated
with late D veins occurring in the inferred center of the heat
source, in contrast with higher iron content observed at the
low-temperature margins of the systems (Alva Jimenez, 2011;
Cohen, 2011). In addition, some trace elements, such as Li,
Sc, Ti, V, Rb, Cs, and Sn, show variations depending upon
the composition of the original mineral replaced by white
mica (Alva Jimenez, 2011). Other studies of alteration miner-
als such as chlorite, biotite, and epidote have proposed the
enrichment of iron relative to aluminum under oxidizing con-
ditions in porphyry-derived fluids close to the mineralized sys-
tem (Cooke and Simmons, 2000; Frikken et al., 2005; Cooke
et al., 2014; Wilkinson et al., 2015).
Compositional variations due to the substitution of octa-
hedral Al3+ by other cations such as Fe2+ and Mg2+ have been
recognized in micas using short-wave infrared spectroscopy.
In general, micas have a deep and diagnostic spectral absorp-
tion feature between 2,185 and 2,230 nm (the 2,200-nm
absorption feature), which is related to the combination of
Al-OH bending and OH stretching vibration modes (Clark et
al., 1990). The wavelength position of this absorption feature
varies as a function of the Al3+ content in the octahedral sheets
and has been used to define the different mineralogical spe-
cies (Swayze et al., 1992; Duke, 1994). Micas with high con-
tent of octahedral Al3+ and interlayer Na+ (e.g., paragonites)
are characterized by shorter-wavelength Al-OH absorptions,
generally between 2,185 and 2,196 nm. Conversely, micas
with relatively lower octahedral Al3+ and higher Si4+, Fe2+, or
Mg2+ (e.g., celadonites) produce Al-OH absorptions in longer
wavelengths, typically between 2,211 and 2,225 nm (Post and
Noble, 1993). White micas such as aluminoceladonites and
muscovites are characterized by the Al-OH wavelength from
2,196 to 2,211 nm (Graham et al., 2018).
Mining and Exploration History
The Copper Cliff deposit is an intermediate-stage explora-
tion project of Kennecott Exploration Company located 48
km east-southeast from Missoula, Montana, at the approxi-
mate coordinates of 46°48.1’N, 113°27.2’W (Fig. 1). Initial
entry into the area was in 1891 as part of the discovery of
placer gold at Bearmouth, with subsequent identification of
oxidized replacement ore associated with fault zones at Cop-
per Cliff (Fairbanks, 2009). Small-scale underground mining
is documented as early as 1900, with an estimated production
of 100,898 lbs Cu, 259 oz Au, and 567 oz Ag (Sahinen, 1957;
Kauffman, 1963) from at least four mines (e.g., Copper Cliff,
Crescent, Tiger, and Leonard). Modern exploration started
intermittently in 1980, when Anaconda Minerals outlined a
deep, high-grade copper-gold porphyry target with potential
resources of 340 Mt of 1.0% Cu and 0.28 g/t Au (C.A. Bran-
non, unpub. report, 1982). Most recently, Kennecott Explora-
tion initiated an exploration program in 2006 to the present
with approximately 32,000 m of diamond drilling comprising
25 holes to depths between 880 and 2,020 m.
 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1271

Fig. 1. Detailed geology map of the Copper Cliff deposit (modified from Lonn, 2007; Fairbanks, 2009). Points represent the loca-
tion of Kennecott Exploration drill holes, and the solid line represents the geology cross section in Figure 2. Coordinate system
WGS 1984 UTM Zone 12N. Inset shows the location of the Copper Cliff deposit in western Montana, United States. Abbrevia-
tions: ID = Idaho, MT = Montana, OR = Oregon, WA = Washington, WY = Wyoming.

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 1272 URIBE-MOGOLLON AND MAHER
Regional Geology and Tectonic Setting
The Copper Cliff prospect is situated within the Montana
thrust belt province along the Lewis and Clark line (Fig. 1).
The area was defined by Billingsley and Locke (1941) as a
wide region in western Montana characterized by a series
of WNW- to ENE-striking thrust faults that transect the
Middle Proterozoic Belt basin (Wallace et al., 1990). The
Middle Proterozoic Belt Supergroup is an intracratonic rift
basin composed of a thick (~18 km) sequence of siliciclastic
rocks, mainly mudstones, siltstones, quartz sandstones, and
limestones (Ross and Villeneuve, 2003). These rocks were
deposited from 1470 to 1401 Ma (Link et al., 1993) over the
Archean and Paleoproterozoic crystalline basement as a result
of hinterland rifting inboard of a compressional orogenic belt
precursor of Rodinia (Winston and Link, 1993). During the
East Kootenay orogeny at 1370 Ma, the Belt Supergroup in
the study area was affected by burial diagenesis and green-
schist metamorphic facies, with metamorphic peak condi-
tions estimated at 690°C and 6.5 kbar, corresponding to ~20
km of burial (Ernst, 1992; Lydon, 2004; Zirakparvar et al.,
2010; Nadoll et al., 2012). A change in the extensional tec-
tonic regime to a more compressional environment during the
Mesozoic to early Tertiary produced the emplacement of a
number of batholiths, including the Pioneer and Philipsburg
batholiths of southwestern Montana, the Boulder batholith
near Butte, the Garnet stock, and the Copper Cliff compos-
ite pluton (Reynolds, 1991; Ellsworth, 1993; Fairbanks, 2009;
Nadoll et al., 2012). Several important hydrothermal ore
districts occur along the Lewis and Clark line, including the
Philipsburg polymetallic/skarn and Butte porphyry Cu-Mo
districts, which are spatially and genetically related to associ-
ated intrusive bodies.
Copper Cliff Geology
Wall rocks-sedimentary units
The Copper Cliff system is hosted within the metasedi-
ments of the Middle Proterozoic Belt Supergroup, mainly
the McNamara and the Garnet Range Formations, which
are unconformably overlain by Cambrian shales of the Silver
Hill Formation and limestones from the Hasmark Forma-
tion (Fig. 1; Fairbanks, 2009). Surface expressions of the
­McNamara Formation consist of interbedded light-green
and red siltite and argillite, with laminated to crossbedded
quartzite (Vuke et al., 2007). The Garnet Range Formation is
primarily composed of dark-green, micaceous, fine-grained
quartzite interbedded with minor argillite (McGroder,
1984). These formations have been grouped by exploration
geologists into a single wall-rock unit as quartzite, with a
minimum thickness of 1,765 m, as observed in drill core.
The Silver Hill Formation comprises brown to a very light
gray banded calcareous shale interbedded with laminated
limestone, whereas the Hasmark Formation is mostly light-
gray or bluish-gray limestone and dark-gray calcareous shale
(Vuke et al., 2007). Total thickness of the shale and lime-
stone units in the district is up to 140 m.
The Copper Cliff intrusive complex
The Copper Cliff intrusive complex comprises several small
and elongated 0.45- to 0.72-km-diameter igneous bodies,
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oriented along an east-northeast trend, consistent with the
regional deformation style (Fig. 1; Ellsworth, 1993; Cox et
al., 1998; Mann and Sears, 2004; Fairbanks, 2009). The larger
igneous bodies are recognized in a district-scale air magnetic
survey by high magnetic intensity features, which overlap a
broad and moderate-intensity feature interpreted to reflect
a deeper batholithic body (Kennecott Exploration, unpub.
report, 2013). Whole-rock geochemical analyses reported
by Ellsworth (1993) indicate quartz latite composition for
the majority of the intrusions. Textural features and cross-
cutting relationships of the intrusive rocks indicate at least
three main age groups: (1) porphyry 1A, corresponding to
intrusive dikes and small stocks emplaced during the main
alteration and mineralization event. They are characterized
by medium-grained, subequigranular textures with a phe-
nocryst to groundmass ratio of 70:30, where the phenocrysts
are mainly composed of plagioclase, hornblende, biotite, and
quartz; (2) porphyry 1B, which corresponds to a later intrusive
stage texturally undistinguishable from that of porphyry 1A,
with fine- to medium-grained phenocrysts composed mainly
of plagioclase, hornblende, and biotite with no quartz; and (3)
porphyry 2, corresponding to postmineral dike(s), emplaced
after the main alteration and mineralization event, charac-
terized by a sparse porphyritic texture with a phenocryst to
groundmass ratio of 30:70 and similar mineralogy to porphyry
1B (Fig. 2). Geochemical distinctions between the major
intrusive types indicate that rocks from porphyry 1A are the
most petrochemically evolved rocks with relative low Cr, Ni,
and V content (Kennecott Exploration, unpub. report, 2013).
They are observed generally in the deeper portions of the drill
holes and at the center of the intrusive system, associated with
potassic alteration and widespread early green phyllic altera-
tion. Locally, they are overprinted by the late white phyllic
alteration associated with quartz-sulfide veins, as well as struc-
turally controlled advanced argillic alteration. Intrusive rocks
from porphyry 1B are petrogenetically similar to porphyry
1A, but with higher content of Cr, Ni, and V. This rock type
occurs as an elongated steeply dipping dike-like body with an
unknown east and west extent. Potassic and early green phyl-
lic alteration styles are also associated with this rock type at
the center of the system, but it is mostly affected to the west
by late white phyllic alteration and advanced argillic alteration
overprinting propylitic alteration (Fig. 2). Porphyry 2 intru-
sive rocks are scarce and present as small dikes with higher
content of Cr, Ni, and V relative to porphyry 1A and 1B, and
with variable degrees of late-stage alteration (e.g., late white
phyllic, advanced argillic, and propylitic).
Copper Cliff breccia
A large mass of hydrothermal/intrusive breccia surrounds
porphyry 1A. The breccia is interpreted to have formed syn-
chronously with the intrusion of porphyry 1A, but the major-
ity of it predates porphyry 1B. It contains clasts of porphyry
1A along with fragments of the Belt Supergroup sediments
within a matrix of magmatic material. This material appar-
ently grades outward into a sediment clast-dominated breccia,
with minor igneous content. Clasts of porphyry 1A observed
within the Copper Cliff breccia are generally highly altered
with potassic, phyllic, and advanced argillic alteration mineral
assemblages.
 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1273

LITHOLOGY
Porphyry 1A
Porphyry 1B
Copper Cliff Breccia
Belt Supergroup
Union Creek Fault
>0.5% Cu
Drill trace

ALTERATION
Supergene
Advanced Argillic
Early Green Phyllic
Late White Phyllic
Potassic
Propylitic

Fig. 2. Interpretive and simplified Copper Cliff deposit cross section shown as A-A' line in Figure 1. Lithology and hydrothermal
alteration showing the mineralized center. Geology and alteration are based on drill holes, some of which (CC11, CC10, and
CC5) are projected onto the section from up to 200 m (see Fig. 1). Porphyry 2 cannot be shown on the section at this scale. Verti-
cal datum is sea level. The coordinate system in the horizontal scale is WGS 1984 UTM Zone 12N.

Structural Geology is associated with higher-grade hypogene copper mineraliza-

The most significant structural feature affecting the Cop-
per Cliff system is the Union Creek fault (Figs. 1, 2), which
displays right-lateral oblique slip (Ellsworth, 1993). Total
normal displacement along this W-dipping fault is approxi-
mately 460 m, juxtaposing deep-level hydrothermal altera-
tion zones (e.g., potassic and green phyllic alteration styles)
in the footwall on the east side, with shallow parts of the
system (e.g., late white phyllic alteration and advanced argil-
lic alteration) in the hanging wall on the west at the surface
(Ellsworth, 1993). The juxtaposition of different levels of
hydrothermal zones is especially evident on the east side of
the Union Creek fault, affecting mostly the intrusive body
of porphyry 1B. Other structural features include numerous
NE-striking faults of lesser offset, which are connected to
the Union Creek fault and probably related with dilational
jogs (Fig. 1; Ellsworth, 1993).
Hydrothermal Alteration
Hydrothermal alteration associated with the Copper Cliff
intrusive complex includes hypogene and supergene altera-
tion assemblages (Fig. 2). The oldest alteration styles
observed are potassic alteration and early-phase phyllic altera-
tion characterized by pervasive to mottled green mica, which
tion. Propylitic alteration occurs in distal zones, and advance
argillic alteration is typically observed in structurally higher
settings, superimposed over earlier alteration types. A late
phase of phyllic alteration associated with quartz-pyrite vein-
ing is observed crosscutting potassic, early green phyllic, and
propylitic alteration assemblages and either predates or is syn-
chronous with advanced argillic alteration (Fig. 2). Supergene
alteration characterized by low-temperature clays and oxida-
tion of sulfides extends up to 300 m below the surface.
Hypogene alteration
Potassic alteration: Potassic alteration has been observed
mainly at depth within the core of both porphyry 1A and 1B,
typically overprinted by other types of alteration, in particu-
lar by the early phase of the phyllic alteration and locally by
advanced argillic alteration. Thin-section petrography shows
K-feldspar and plagioclase phenocrysts altered to secondary
feldspar, locally associated with patches of anhydrite and/or
calcite. Hydrothermal biotite has nearly completely replaced
hornblende phenocrysts, whereas it only rims magmatic bio-
tite. Anhydrite also occurs as disseminated grains or within
early dark micaceous bands (EDM veinlets as per Meyer et
al., 1968) and quartz ± K-feldspar veinlets. Minor magnetite
generally is found within altered mafic phenocrysts and within

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 1274 URIBE-MOGOLLON AND MAHER

early quartz veinlets. Copper minerals chalcopyrite and born-
ite are found locally in hairline fractures.
Phyllic alteration: Based on drilling to date, the two stages
of phyllic alteration are the most common and widely dis-
tributed alteration assemblages (Figs. 2, 3). The early green
alteration is observed locally overprinting the potassic alter-
ation at the margins and above the porphyry 1A but also
appears locally as an assemblage of white mica ± K-feldspar
± hydrothermal biotite ± anhydrite. This alteration style is
commonly pervasive and locally texturally destructive, result-
ing in a mottled appearance composed of mixed fine-grained
gray- to green-colored mica ± quartz ± specular hematite ±
rutile (Figs. 3A-C, 4A). Where relic textures can still be dis-
cerned, plagioclase phenocrysts are strongly altered to white
mica, locally associated with patches of calcite ± anhydrite;
mafic phenocrysts are replaced by white mica ± specular
hematite ± rutile, and in some cases chlorite is present; and
groundmass is composed of fine-grained quartz. Samples with

A B

2 cm 2 cm

C D

2 cm 2 cm

Fig. 3. Drill core photos showing the two styles of phyllic alteration at Copper Cliff. A) Sample with strong pervasive and textur-
ally destructive early green phyllic alteration. Note the green-gray-colored mica associated with fine-grained specular hematite
and disseminated chalcopyrite. B) Sample from the early green phyllic alteration style showing mottled texture. C) Strongly
silicified sample associated with the early green phyllic alteration. D) Sample with late white phyllic alteration associated with
a quartz-pyrite vein. Note the white-colored mica replacing plagioclase phenocrysts and yellow-colored mica associated with
mafic phenocrysts with a generally preserved igneous texture.

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 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1275

A B
cpy and

cpy

hem
anh hem
0.5 mm 0.5 mm

C D
bt rt

py

pl

bt
0.5 mm 0.5 mm

Fig. 4. Photomicrographs of phyllic alteration in cross-polarized light. A) Mottles of mica from the early phyllic alteration style
with patches of anhydrite (anh), specular hematite (hem), and disseminated fine-grained chalcopyrite (cpy). B) Hydrothermal
andalusite (and) with specular hematite and fine-grained chalcopyrite in a silicified sample from the early green phyllic alteration
style. C) Pseudomorphs of plagioclase (pl) and biotite (bt) phenocrysts completely replaced by white mica (±rutile in biotite) in
the late phyllic alteration, with minor disseminated fine-grained pyrite (py). D) Biotite phenocryst fully replaced by white mica
and rutile (rt) in the late phyllic alteration. The yellowish color of mafic phenocrysts observed in hand samples from the late
phyllic alteration style is attributed to secondary fine-grained rutile.

intense alteration are strongly silicified with clots of andalusite
and specular hematite associated with white mica and kaolin-
ite (Fig. 4B). The early green alteration is generally related
with the highest hypogene copper grades (>0.5% Cu), con-
stituting the assemblage of chalcopyrite ± bornite with lesser
pyrite. Expressions of this alteration are observed locally in
porphyry 1B and characterized by the assemblage of white
mica ± K-feldspar ± hydrothermal biotite ± anhydrite, sug-
gesting contemporaneity with the potassic alteration. The
early phyllic alteration in porphyry 1B only contains subeco-
nomic grades of copper mineralization. The distal expression
of the early phyllic alteration consists of the assemblage of
white mica ± quartz ± specular hematite ± rutile but is not
texturally destructive and is effectively unmineralized.
The late phyllic alteration is observed in both porphyry
1A and 1B, overprinting potassic, early green phyllic, and
propylitic alteration phases. It is locally present as up to
10-cm-thick halos about quartz-pyrite veins (D veins as per
Gustafson and Hunt, 1975), typically with preservation of
the original rock texture. Alteration of this type shows pla-
gioclase phenocrysts replaced by white-colored mica and
mafic silicates altered to yellow-colored mica ± pyrite ±
rutile (Figs. 3D, 4C). The overall yellowish color is appar-
ently produced by residual fine-grained Ti oxides such as
rutile, which is usually associated with relics of mafic phe-
nocrysts (Fig. 4D). Disseminated fine-grained pyrite (up to
5 vol %) is present, usually as subhedral grains. Copper con-
centrations in this alteration assemblage are typically low;
only trace amounts of chalcopyrite (and locally molybdenite)
are present in the quartz-pyrite veins. In zones where the
late phyllic alteration is superimposed on mineralized early
green phyllic alteration, Cu sulfide destruction occurred.
Expressions of the late phyllic alteration are also present in
rocks of the Belt Supergroup, usually as 2-cm-thick halos
associated with faint quartz-pyrite veins.
Advanced argillic alteration: Advanced argillic alteration
occurs at the surface above the highest-grade mineralized
zone and extends along structures to depth in the system.

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 1276 URIBE-MOGOLLON AND MAHER
It overprints the early green phyllic and potassic alteration
zones and reaches up to 1,448 m below ground surface in the
western parts of the system. The mineral assemblage consists
of alunite ± quartz ± kaolinite ± dickite ± pyrophyllite, asso-
ciated with variable amounts of disseminated pyrite (up to
1  vol %) (Fairbanks, 2009). Massive pyrite veins over 10 to
15 cm thick are observed locally, usually associated with minor
hypogene chalcopyrite, bornite, or enargite (Pardee, 1918).
Microscopic electrum inclusions occur within pyrite grains in
advanced argillic alteration (Fairbanks, 2009).
Propylitic alteration: Propylitic alteration at Copper Cliff is
most abundant at the peripheral margins of the main porphyry
1B. Rocks with propylitic alteration have a yellowish-green
appearance. The alteration assemblage includes chlorite ±
montmorillonite ± calcite ± pyrite. Chlorite replaced mafic
phenocrysts, and montmorillonite and minor calcite replaced
plagioclase. Fine-grained pyrite (<1 vol %) may be present.
Supergene alteration
A leached cap probably produced by supergene weather-
ing and/or hydrothermal acid alteration extends up to 300 m
below the surface. It is characterized by abundant kaolinite ±
montmorillonite in addition to iron oxides that replace pre-
existing sulfides along fractures. Appreciable amounts of Cu
oxides along with residual enargite, luzonite, and famatinite
have been recognized in the leached cap near the surface
(Pardee, 1918; Sahinen, 1957).
Mineralization
Chalcopyrite and bornite occur mostly as very fine grained
(<1 mm) disseminations within the porphyry 1A and 1B but
also within the hydrothermal/intrusive breccia. Chalcopyrite
is present as disseminated anhedral grains, typically asso-
ciated with specular hematite and only locally with minor
pyrite. Bornite partially replaced chalcopyrite but in some
cases appears to have coprecipitated with chalcopyrite in the
presence of specular hematite. Minor hypogene chalcocite
replaced bornite (Fairbanks, 2009).
Copper sulfides in porphyry 1A are typically associated with
early green phyllic alteration. Copper assays for the freshest
(unaltered) versions of this porphyry average approximately
1,000 ppm, with the higher grades (>0.5% Cu) mainly distrib-
uted in the eastern central portion of the system below 950 m
depth intercepted by drill holes CC10 and CC13. In the early
green phyllic alteration phase, fine-grained specular hematite
is commonly present, except where it is influenced by sul-
fidation related to the late phyllic alteration. In the potassic
alteration, minor chalcopyrite and bornite are present as fine-
grained disseminations within biotite-replaced mafic pheno-
crysts and anhydrite clots. Granular and non-throughgoing
quartz veinlets with chalcopyrite and bornite are also pres-
ent locally. Mineralization of porphyry 1B was weaker than in
porphyry 1A. Copper assays for freshest examples of 1B rock
average approximately 600 ppm, with low-grade mineraliza-
tion present below 1,200 m depth intersected in hole CC8.
Mineralization of porphyry 1B is spatially associated with
potassic alteration and early green phyllic alteration, which
appear to be contemporaneous in that rock type. Copper min-
eralization occurred in late structures with advanced argillic
alteration, such as chalcopyrite, bornite, or enargite, and may
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represent the deposition of copper remobilized from else-
where in the system.
Age Dates
All geochronological data available from Copper Cliff deposit
is shown in Fig. 5. Nine U-Pb dates obtained on zircons con-
strain the crystallization age of the Copper Cliff intrusive com-
plex from 48.66 to 47.14 Ma (Kennecott Exploration, unpub.
report, 2014). Intrusive phases of porphyry 1A range in age
from 48.6 ± 0.73 to 48.4 ± 0.71 Ma. Porphyry 1B is later than
porphyry 1A and ranges in age from 48.03 ± 0.72 to 47.9 ±
0.61 Ma. One intrusive phase from porphyry 2 was dated at
47.1 ± 0.65 Ma. The age of the late white phyllic event was
defined by two identical Re-Os ages of 49.6 ± 0.2 Ma obtained
from associated molybdenite (Kennecott Exploration, unpub.
report, 2014). Two samples of alunite from the advanced
argillic alteration halo around the mineralized zone yielded
40Ar/39Ar plateau ages of 49.8 ± 0.27 and 42.64  ± 0.37  Ma
(Kennecott Exploration, unpub. report, 2014). A similar age
of 48.4 ± 1.3 Ma for the acid-sulfate epithermal alteration was
reported by Ellsworth (1993) based on K-Ar in alunite. There-
fore, the older alunite 40Ar/39Ar age is considered acceptable
and suggests a genetic relationship between the late white
phyllic alteration event and the advanced argillic alteration.
The younger alunite 40Ar/39Ar age is not consistent with the
rest of the geochronological data of the system, and it is inter-
preted to be the product of apparent 40Ar loss. Considering
the inherent problems, particularly when comparing different
isotopic systems for geochronology, the data presented here
and in Figure 5 indicate that emplacement of the Copper
Cliff intrusive complex and alteration/mineralization events
are coeval within analytical error, suggesting that all occurred
at about the same time.
Samples and Analytical Methods
Detailed core logging of the lithology, alteration, and mineral-
ization at Copper Cliff was conducted on 16 drill holes across
the district (Fig. 1). Samples of the different phyllic altera-
tion styles were taken from drill core at a minimum interval
of 100 m within each drill hole based on prior geologic infor-
mation gathered from drill logs. A total of 100 core samples
corresponding to the most representative phyllic alteration
were collected from porphyries 1A and 1B. Hyperspectral
mineral maps were acquired on-site from few drill core sam-
ples using Corescan’s Hyperspectral Core Imager Mark  III
(HCI-3) system. The Corescan imaging spectrometer col-
lects spectral data in reflectance in the wavelength range of
350 to 2,500  nm at a spatial resolution of 0.5 mm. Mineral
maps produced by the Corescan imaging spectrometer were
used to evaluate qualitatively the distribution and wavelength
positions for white mica. Thin-section petrography of all core
samples was undertaken using transmitted and reflected light.
In order to evaluate the presence of clay minerals, a set of
four samples was analyzed by X-ray diffraction. In addition,
40Ar/39Ar geochronology was conducted on handpicked white
mica from two samples corresponding to the early green phyl-
lic alteration phase and two from the late white phyllic style.
40Ar/39Ar dates were obtained using conventional double-vac-
uum furnace step-heating methods (Heizler et al., 1999). The
X-ray diffraction and 40Ar/39Ar geochronology analyses were
 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1277

Ma

AA
EGPA LWPA (40Ar-39Ar)
Porphyry 1A (Re-Os)
50 (Zircon U-Pb) (40Ar-39Ar)

LWPA
Porphyry 1B (40Ar-39Ar)
(Zircon U-Pb)
49

48

47

Porphyry 2
(Zircon U-Pb)
46
Fig. 5. Summarized geochronological data for the Copper Cliff deposit. Crystallization U-Pb zircon ages for the intrusive rocks
fall into three age groups. Intrusive phases of porphyry 1A range in age from 48.6 to 48.4 Ma. Intrusive phases of porphyry 1B
range in age from 48.03 to 47.9 Ma. Porphyry 2 was dated at 47.1 ± 0.65 Ma. Alteration and mineralization events are coeval
within analytical error to the emplacement of porphyry 1A. The gray boxes represent the measurement uncertainty. Abbrevia-
tions: AA = advanced argillic alteration, EGPA = early green phyllic alteration, LWPA = late white phyllic alteration.

carried out at the New Mexico Bureau of Geology and Min-
eral Resources.
Using thin-section billets, 43 samples were prepared as pol-
ished resin mounts for electron microprobe analysis (EMPA)
and laser ablation-inductively coupled plasma-mass spec-
trometry (LA-ICP-MS). Major element analyses of individual
crystals of white mica were obtained using a Cameca SX100
electron microprobe at the facilities of the New Mexico Bureau
of Geology and Mineral Resources. The analyses were per-
formed on five crystals per sample with a beam size of 10 µm,
an accelerating voltage of 15 kV, and a beam current of 20 nA.
Since the early phyllic alteration style is commonly texturally
destructive where most intense, recognition of a precursor
mineral phase to the white mica could not be ascertained,
and so sample locations were taken at random. In the late
phyllic alteration it is generally possible to determine the
mineral phase replaced by mica due to textural preservation,
and so in this case the focus of analysis was on white mica
that replaced plagioclase phenocrysts. Trace element concen-
trations in the same grains were determined using a 193-nm
ultrashort pulse excimer laser ablation workstation coupled to
a Bruker 820-MS inductively coupled plasma-mass spectrom-
eter, located in the Corman Center for Mass Spectrometry
at Rensselaer Polytechnic Institute, New York. In total, 167
LA-ICP-MS spot analyses were acquired using typically three
to five spot analyses from each sample, with a 100-µm beam
size and a laser pulse frequency of 10 Hz. The NIST-612 glass
standard was used for external calibration, and Si was used as
the internal standard. Data reduction was conducted by visual
inspection and using the Lolite software package for Igor Pro
6.37 at the Rensselaer Polytechnic Institute facilities (Paton
et al., 2011).
Point-based visible to near-infrared (VNIR) and short-wave
infrared (SWIR) reflectance spectra between 350 and 2,500
nm were collected from the billets of the thin sections using
Spectral Evolution’s OreXpress™ field portable spectrometer
located at the New Mexico Institute for Mining and Technol-
ogy. In total, 336 4-mm-diameter spot analyses were obtained,
consisting of five to seven spots per billet on a transect, to
identify compositional variations of white mica over the alter-
ation system and on the scale of an individual sample. The
white reference measurement and optimization of the instru-
ment were conducted every ~15 min. In addition, the repro-
ducibility of the instrument was evaluated by measuring 10
times the same spot in a standard under identical conditions
every ~90 min. To obtain a 4-mm-diameter spot analyses,
an opaque mask was attached to the mineral contact probe.
The opaque mask allows a reduction of the standard 20-mm-
diameter analytical spot size, though still preserving sufficient
reflectance intensity to permit the identification of minerals
using SWIR absorption spectra features. The 4-mm-diame-
ter spot analyses are useful to discriminate different styles of
phyllic alteration overprinting a single sample and to allow for
the clear identification of absorption feature shifts over small
spatial scales (Maher and Wallace, 2017). The spectrometer is
factory calibrated. Interpretation of each spectrum was con-
ducted using The Spectral Geologist Software™ (TSG; ver-
sion 7.1.0.062) after performing the Hull quotient calculation.

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 1278 URIBE-MOGOLLON AND MAHER

The wavelength positions of the white mica absorption fea-
ture at ~2,200 nm were extracted using a graphic extrapola-
tion approach in Microsoft Excel®.
Results
Characterization of the white mica SWIR spectra
The reflectance spectra of both styles of phyllic alteration in
the Copper Cliff system show well-expressed absorption fea-
tures in the VNIR-SWIR region. The statistical data in Figure
6 show two populations of white micas based on the wave-
length variation of the 2,200-nm Al-OH absorption feature.
The first population is related to the late white phyllic altera-
tion style and is characterized by band centers ranging from
2,197 to 2,207 nm. The histogram shows a normal distribution
with mean value at 2,201 nm and the most common absorp-
tion feature located at 2,202 nm, with 25 counts out of 130.
The second population is related to the early green phyllic
alteration style, which shows a negatively skewed distribution
60 LW PA
n=130
Mean=2201
40 Median=2201
Count
with band centers between 2,201 and 2,210 nm, with the
median absorption feature located at 2,208 nm. Reproduc-
ibility of the measured band center is approximately ±2 nm,
shown by the (1σ) standard deviation of 10 repeated analyses
on the same spot.
Samples from the early green phyllic alteration style with
white mica band centers shorter than 2,207 nm show late
white phyllic alteration overprint and/or IR absorption evi-
dence for the presence of kaolinite. Mixed reflectance spectra
of white mica with kaolinite is identified by the shape of the
Al-OH absorption feature, which tends to be relatively broad
and asymmetrical with a weak inflection toward 2,162  nm
compared with the single sharp and symmetric feature of
samples with white mica with no kaolinite (S. Halley, unpub.
report, 2016). Furthermore, the position of the Al-OH absorp-
tion feature of white micas mixed with kaolinite is shifted to
shorter wavelengths, which explains the negatively skewed
distribution of the early green phyllic alteration. Kaolinite was
also identified by petrographic analyses as pale brown-colored
replacement patches within the white mica mottles, typically
with low to moderate relief. The presence of kaolinite was
confirmed in the X-ray diffraction analyses.
Differences in the apparent white mica band centers
between the two distinctive phyllic alteration styles at Cop-
per Cliff are observed in the mineral maps produced by the
Corescan™ system (Fig. 7A) and the Hull quotient spectra
collected by the OreExpress™ (Fig. 7B, C). The reflectance

Mode=2202 spectra of mica from the early green phyllic alteration is com-
δ=2.39 monly characterized by the Al-OH spectral absorption feature
centered around the 2,208-nm region and three broad intense
20 absorption features located around 715, 890, and 1,100 nm,
with a steep slope toward longer wavelengths (Fig. 7B). A
weak absorption feature is also noted near 2,250 nm, usually
displayed in the form of a faint inflection or shoulder. Another
0 important characteristic of the reflectance spectra of mica
from the early green phyllic alteration is that approximately
60 EGPA half of the analyzed samples present a deep-water absorption
component near 1,900 nm. The depth of this water absorption
n=206 feature is almost the same as the main Al-OH absorption fea-
Mean=2208 ture, implying an important illitic component in the spectra.
40 Median=2208 Unlike spectra from the early green phyllic alteration, white
Mode=2209 micas from the late phyllic alteration style are characterized
δ=2.15 Mixed with by the Al-OH spectral absorption feature centered around the
kaolinite 2,201-nm region and weak electronic absorptions in the VNIR
20 and/or LWPA region between 715 and 1,100 nm (Fig. 7C). In addition, the
overprint water absorption feature near 1,900 nm is only observed in
one-third of the analyzed samples and presents variable inten-
sities but is generally less deep than samples from the early
0
green phyllic style.
The SWIR data collected with the OreExpress™ from a
billet sample show the transition of the spectra from the late
21 6
97

21 8
22 9
22 0
22 1
02

22 3
04

22 5
22 6
22 7
22 8
09

22 0
11
9

9
9
0
0

0
0
0
0

1
21

21

22

22

22

white phyllic alteration to the early green phyllic alteration

Wavelength (nm)
Fig. 6. Histogram plot of the early and late phyllic alteration events based on
the wavelength position of the Al-OH band centers collected with the OreEx-
pressTM spectrometer. The late white phyllic alteration (LWPA) samples have
Al-OH band centers with wavelengths from 2,197 to 2,207 nm. Band centers of
the early green phyllic alteration (EGPA) range between 2,201 and 2,210 nm.
Samples from the early green phyllic alteration style with band centers shorter
than 2,207 nm show evidence of kaolinite and/or late phyllic alteration over-
print according to petrographic and X-ray diffraction analyses.
styles (Fig. 8). Spectra A to D correspond to the late white
phyllic style, and spectra E to G are associated to the early
green phyllic alteration. The Al-OH band centers from the
late phyllic alteration show a progressive increase in wave-
length from 2,200 nm at the border of the billet to 2,202 nm
in proximity to the quartz-pyrite veinlet. In contrast, spectra
from the early green phyllic style in the sample have Al-OH
band centers with wavelengths from 2,208 to 2,209 nm.

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 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1279

A B
EGPA SWIR
1

0.95

0.9

HullQuot
0.85 2250 nm
MgFe 3+
0.8 MgAl

2209 nm
0.75 Electronic processes Al-OH
Fe 2+, Fe 3+

0.7
500 1000 1500 2000 2500
Wavelength (nm)

C
LWPA SWIR
1

0.95

0.9
HullQuot

1 cm 0.85

0.8 1410 nm
OH 2201 nm
White Mica: 2200 nm Wavelength Position
0.75 Al-OH

2197nm 2212nm
0.7
500 1000 1500 2000 2500
Wavelength (nm)
Fig. 7. A) Mineral map produced from Corescan imaging spectrometer scan of a sample from Copper Cliff with early green
phyllic alteration in the upper part of the sample and late white phyllic alteration in the lower part. Note the differences of the
positions of the white mica band centers between the two styles of phyllic alteration. The black circles represent the points ana-
lyzed by the OreExpressTM spectrometer. B) Hull quotient spectra of white mica from the early green phyllic alteration (EGPA).
The three intense absorption features located around 715, 890, and 1,100 nm are probably associated with crystal field effects
(Burns, 1993) and the absorption feature near 2,250 nm to MgFe3+ and MgAl cation pairs bonded to OH groups in the structure
of white micas (Swayze et al., 2018). C) Hull quotient spectra of white mica from the late white phyllic alteration (LWPA). SWIR
= short-wave infrared.

Hydrothermal geochronology complexity caused principally by excess argon, as the oldest

New 40Ar/39Ar dates obtained from white micas correspond-
ing to the early green (CC13-1078, CC10-1074) and late
white phyllic (CC18-1881, CC17-1093) alteration styles
show relatively complex patterns characterized by initial
young ages that climb steeply to maximum values of about
57 to 55 Ma over the first few percent of 39Ar released and
then steadily decline in age until the final 10 to 15% of the
spectrum where the ages become constant at about 50 to
49 Ma (Fig. 9; Digital App. 1). The age spectrum complex-
ity likely has several causes, where the initially young ages
could result from 39Ar recoil implantation into nonreten-
tive low-K phases (e.g., clay) or record argon loss follow-
ing initial crystallization. The ages that approach 55 Ma or
greater are older than the intrusive rocks and could result
from 39Ar recoil ejection during irradiation and/or excess
40Ar. Isochron analysis (Fig. 10) supports the age spectrum
apparent ages are inversely correlated with the radiogenic
yield—that is, as apparent ages decrease across the spec-
tra while the radiogenic yield increases. The isotope corre-
lation arrays have high mean square of weighted deviates
(MSWD) values owing to probable mixing between atmo-
spheric and excess argon trapped components, but project
to ages between 51and 48 Ma (Fig. 10). These isochron ages
are similar to the final heating steps of the age spectra and
support the general validity of the isochron ages.
Geochemical composition of white micas
Major elements variation: The chemical composition of white
micas was analyzed by electron microprobe wavelength dis-
persive analysis (EMPA). Representative analytical results
are summarized in Table 1, and reproducibility and detection
limit can be found in Table A1 of the Digital Appendix. In this

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 1280 URIBE-MOGOLLON AND MAHER

A Point 1 E Point 5
0.8

0.8
Norm. HullQ

Norm. HullQ
0.4

0.4
Al-OH Al-OH
2200 nm 2208 nm
0

800 1200 1600 2000 2400 800 1200 1600 2000 2400
Wavelength in nm Wavelength in nm

B Point 2 F Point 6

0.8
0.8

Norm. HullQ
Norm. HullQ
0.4

0.4

Al-OH Al-OH
2200 nm 2209 nm

800 1200 1600 2000 2400 800 1200 1600 2000 2400
Wavelength in nm Wavelength in nm

C Point 3 G Point 7
0.8

0.8
Norm. HullQ

Norm. HullQ
0.4

0.4

Al-OH Al-OH
2202 nm 2209 nm
0

800 1200 1600 2000 2400 800 1200 1600 2000 2400
Wavelength in nm Wavelength in nm

D Point 4
0.8
Norm. HullQ
0.4

Al-OH
2202 nm
0

800 1200 1600 2000 2400 1 cm

Wavelength in nm

Fig. 8. Short-wave infrared cross section illustrating the variation in wavelength of the Al-OH band center of white micas from
the early green and the late phyllic alteration styles. Points 1 to 4 correspond to spectra A to D from the late white phyllic altera-
tion. Points 5 to 7 correspond to spectra E to G from the early green phyllic style. The photograph references the sample locations
along the transect on the billet.

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 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1281

A B

C D

Fig. 9. 40Ar/39Ar age spectra plots for white mica from the early green phyllic alteration and the late white phyllic alteration.
Samples CC13-1078 (A) and CC10-1074 (B) correspond to white mica from the early green phyllic alteration, and samples
CC18-1881 (C) and CC17-1093 (D) correspond to white mica from the late white phyllic alteration. Graphics show complex
age spectra caused by potential 39Ar recoil and/or argon loss. The final heating steps for spectra and weighted mean ages for the
two styles of phyllic alteration are analytically indistinguishable from the 40Ar/39Ar alunite age and the Re-Os ages. All errors are
±2σ. MSWD = mean squarae of weighted deviates.

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 1282 URIBE-MOGOLLON AND MAHER

A B

C D

Fig. 10. Inverse isochron plots for white mica from the early green phyllic alteration and the late white phyllic alteration. Samples
CC13-1078 (A) and CC10-1074 (B) correspond to white mica from the early green phyllic alteration, and samples CC18-1881
(C) and CC17-1093 (D) correspond to white mica from the late white phyllic alteration. Isochron ages support the mean weighted
ages and provide the timing for the phyllic alteration events. All errors are ±2σ. MSWD = mean square of weighted deviates.

study, the structural formula of white micas was normalized
to atoms per formula unit (apfu) on the basis of 11 anhydrous
oxygens, and all iron expressed as formula units was assumed
to be Fe2+ (Newman, 1987). This assumption will be dis-
cussed later. Occupancy of the tetrahedral site is assumed to
be complete when calculating atom formula units.
Microprobe analyses of representative white micas from
the early phyllic alteration style have the compositional range
of (K0.63–0.91Na0.02–0.07)(Fe0.1–0.21Mg0.04–0.55Al1.52–1.87)(Si3.06–3.36
Al0.64–0.94)O10(OH)2. The interlayer cation (K + Na + Ca)
site occupancy ranges between 0.71 and 0.98 apfu (Fig. 11)
and is predominantly potassic, with K varying from 0.63 to
0.91 apfu. The sodium content is relatively low, mostly under
0.07 apfu. Calcium values are mostly below detection limit,
with a few outliers up to 0.065 apfu. In the octahedral site,
Fe + Mg + Mn contents range between 0.16 and 0.60 apfu,
with one outlier at 0.71 apfu. Magnesium content varies from
0.04 to 0.40 apfu, with one outlier at 0.55 apfu. Iron values are
relatively lower than magnesium, with concentrations rang-
ing from 0.1 to 0.21 apfu. Manganese is generally below the

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Table 1. Representative Microprobe Analyses of White Micas at Copper Cliff Expressed on an Anhydrous Basis

CC10- CC10- CC13- CC13- CC7- CC2- CC8- CC13- CC9- CC11- CC5- CC13- CC8- CC4- CC17-
Sample 955-2 1231-1 1078-1 361-1 332-3 72-1 1487-3 1985-1 1063-2 1156-1 355-3 1514-5 1545-1 94-1 610-1

Distance to
deposit center (m) 0 273 351 565 580 841 942 1,170 495 527 665 715 974 986 1,358

Alteration EGPA EGPA EGPA EGPA EGPA EGPA EGPA EGPA LWPA LWPA LWPA LWPA LWPA LWPA LWPA

Wt %
SiO2 44.03 45.34 46.89 51.68 47.83 49.45 47.4 48.74 48.49 46.56 47.53 47.93 45.44 46.05 50.96
TiO2 0.66 0.38 0.34 0.02 0.1 0.13 0.14 0.02 0.02 0.12 0.19 0.15 0.12 0.22 0.15
Al2O3 33.26 34.47 30.85 32.32 30.84 30.91 31.1 30.31 34.18 34.01 33.65 34.49 35.01 32.64 32.85
FeO 3.07 2.79 2.22 2.05 2.37 3.45 1.98 3.72 0.39 1.52 1.7 1.31 0.47 0.95 1.43
MnO 0.01 0.01 <0.01 0.02 <0.01 0.03 <0.01 0.05 <0.01 <0.01 <0.01 <0.01 0.01 <0.01 <0.01
MgO 0.54 0.38 2.88 1.53 2.03 4.15 2.27 2.86 0.34 0.98 1.51 1.33 0.56 2.92 2.04
CaO 0.03 <0.01 0.07 0.22 0.2 0.94 0.08 0.11 0.38 0.07 0.06 0.21 0.16 0.26 0.24
Na2O 0.47 0.5 0.36 0.34 0.2 0.42 0.19 0.22 0.44 0.54 0.43 0.53 0.38 0.53 0.24
K2O 10.29 10.52 10.56 8.84 8.67 7.93 10.24 10.26 8.73 10.33 10.13 10.49 10.63 10.03 8.99
F 0.18 0.09 0.38 0.17 0.15 0.12 0.34 0.17 0.07 0.32 0.53 0.34 0.32 0.58 0.26
Cl 0.03 0.01 0.01 0.01 0.03 0.08 <0.01 0.01 0.11 0.08 0.02 0.03 0.02 0.02 <0.01
O = F,Cl 0.08 0.04 0.16 0.07 0.07 0.07 0.14 0.07 0.06 0.15 0.23 0.15 0.14 0.25 0.11
Total 92.65 94.53 94.72 97.27 92.49 97.68 93.88 96.54 93.21 94.68 95.98 96.96 93.26 94.45 97.05

Structural formulas
Si 3.06 3.07 3.18 3.33 3.26 3.21 3.22 3.24 3.24 3.14 3.16 3.15 3.09 3.12 3.28
AlIV 0.94 0.93 0.82 0.67 0.74 0.79 0.78 0.76 0.76 0.86 0.84 0.85 0.91 0.88 0.72

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AlVI 1.78 1.83 1.65 1.78 1.74 1.58 1.71 1.62 1.93 1.83 1.8 1.81 1.91 1.72 1.78
Ti 0.03 0.02 0.02 <0.01 0.01 0.01 0.01 <0.01 <0.01 0.01 0.01 0.01 0.01 0.01 0.01
Fe 0.18 0.16 0.13 0.11 0.14 0.19 0.11 0.21 0.02 0.09 0.09 0.07 0.03 0.05 0.08
Mn <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
Mg 0.06 0.04 0.29 0.15 0.21 0.4 0.23 0.28 0.03 0.1 0.15 0.13 0.06 0.29 0.2
Σ Oct. 2.05 2.04 2.08 2.04 2.09 2.18 2.06 2.11 1.99 2.02 2.05 2.02 2 2.08 2.06
COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA

Ca <0.01 <0.01 0.01 0.02 0.01 0.07 0.01 0.01 0.03 0.01 <0.01 0.01 0.01 0.02 0.02
Na 0.06 0.07 0.05 0.04 0.03 0.05 0.03 0.03 0.06 0.07 0.06 0.07 0.05 0.07 0.03
K 0.91 0.91 0.91 0.73 0.75 0.66 0.89 0.87 0.74 0.89 0.86 0.88 0.92 0.87 0.74
Σ Int. 0.98 0.98 0.97 0.78 0.8 0.78 0.92 0.91 0.83 0.96 0.92 0.96 0.99 0.95 0.79

F 0.04 0.02 0.08 0.03 0.03 0.02 0.07 0.04 0.01 0.07 0.11 0.07 0.07 0.12 0.05
Cl <0.01 <0.01 <0.01 <0.01 <0.01 0.01 <0.01 <0.01 0.01 0.01 <0.01 <0.01 <0.01 <0.01 <0.01

SWIR (nm) 2,208 2,209 2,209 2,207 2,206 2,208 2,210 2,209 2,198 2,204 2,200 2,205 2,202 2,204 2,202

Note: Number of ions on the basis of 11 oxygens, and all iron as Fe2+
Abbreviations: Σ Int. = sum of interlayer cations, Σ Oct. = sum of octahedral cations, AlIV = calculated tetrahedral Al, AlVI = calculated octahedral Al, EGPA = early green phyllic alteration, LWPA =
late white phyllic alteration, SWIR = short-wave infrafred (wavelength position of the white mica Al-OH band center determined from billet)
1283
 1284 URIBE-MOGOLLON AND MAHER

2.8 3.0 3.2 3.4 3.6 2.0 2.2 2.4 2.6 2.8 3.0 0.00 0.01 0.02 0.03 0.04
Si (apfu ) Al (apfu ) Ti (apfu )

0.00 0.05 0.10 0.15 0.20 0.25 0.0 0.2 0.4 0.6 0.000 0.001 0.002 0.003 0.004

Fe (apfu ) Mg (apfu ) Mn (apfu )

0.5 0.6 0.7 0.8 0.9 1.0 0.00 0.02 0.04 0.06 0.08 0.10 0.00 0.02 0.04 0.06 0.08

K (apfu ) Na (apfu ) Ca ( apfu )

Early Green Phyllic Alteration

Late White Phyllic Alteration

0.6 0.7 0.8 0.9 1.0 1.1 0.0 0.2 0.4 0.6 0.8

K+Na+Ca (apfu ) Fe+Mg+Mn (apfu )

Fig. 11. Compositional variations in major elements for white micas from the early and late phyllic alteration styles. Analysis
of variance (one-way ANOVA) at a 95% confidence level demonstrates significant differences in the content of Al, Fe, Mg,
and Na. The box symbol represents the middle 50% of the data with the mean value (cross), the median (vertical line), and
whiskers are the 5% and 95% values; black dots represent outliers. The numbers of analytical points for the early and late
phyllic alteration are 48 and 31, respectively. apfu = atoms per formula unit.

detection limit. Silicon content ranges from 3.06 to 3.36 apfu,
and total aluminum varies from 2.25 to 2.75 apfu.
White micas from the late phyllic alteration style have
the compositional range of (K0.63–0.93 Na0.02–0.09)(Fe0.02–0.12
Mg0.03–0.29 Al1.68–1.93)(Si3.09–3.43Al0.57–0.91)O10(OH)2. Analysis of
variance (one-way ANOVA) at a 95% confidence level was
conducted to test the significance of the observed differences
in major element concentrations between the two styles of
phyllic alteration (see Digital App. Table A2). The number
of interlayer cations (K + Na + Ca) is statistically similar (p >

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 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1285

0.05) to white micas from the early green phyllic alteration significant, with higher values in white micas from the late
style. No distinct differences were detected between the phyllic alteration in the range of 2.26 to 2.81 apfu.
potassium and calcium contents of the late phyllic altera- The compositional variation of white micas can be explained
tion compared with the values of the early phyllic style. On by four principal substitutions (Cohen, 2011): (1) Tschermak
the other hand, sodium values are slightly higher than white substitution VIAl3+ + IVAl3+ ↔ VIFe2+ + IVSi4+, (2) direct VIFe3+
micas from the early phyllic alteration (p < 0.05), reaching ↔ VIAl3+ substitution, (3) illitic substitution K+ + IVAl3+ ↔ IVSi4+
contents up to 0.09 apfu. In the octahedral site, Fe + Mg + + [ ]interlayer cation site, and (4) direct Na+ ↔ K+ substitution. Com-
Mn shows significantly lower concentrations compared with positionally, 52% of white micas from the early green phyllic
those from the early green phyllic style, with values ranging alteration and 58% from the late phyllic style are aluminocela-
from 0.056 to 0.36 apfu (Fig. 11). The largest differences in donite (Fig. 12A). The term “aluminoceladonite” is defined as
the octahedral site of the late phyllic alteration are observed an intermediate mica with composition between muscovite and
in the magnesium and iron contents, with values ranging from celadonite, characterized by VIR2+/(VIR2+ + VIR3+) ≥ 0.25, VIAl/
0.03 to 0.29 apfu and 0.02 to 0.12 apfu, respectively. Manga- (VIAl + VIFe3+) ≥ 0.5–1.0, and Mg/(Mg + VIFe2+) > 0.5 (Rieder
nese and silicon concentrations are statistically similar in both et al., 1998). In addition, illitic substitution is observed in 48%
alteration styles. In contrast, ANOVA analysis demonstrates of the white micas associated with the early green phyllic style
that differences in the total aluminum values are statistically and 26% of the late white phyllic variety. Illitic substitution in

A Toward Aluminoceladonite B
Celadonite VI
Al + IVAl3+ <-> VIFe2+ + IVSi4+ Muscovite
3+
1.0 0.8
K+ + IVAl3+ <->

EGPA y = -0.7025x
Fe+Mg+Mn (apfu) R2 =0.36
0.9 0.6
K+Na+Ca (apfu)

LWPA y = -0.4957x
R2 =0.33

0.8 0.4
IV 4+
Si + [ ]

VI
Al3+ <-> VIFe3+
0.7 0.2 y = -x
VI
Al3+ + IVAl3+ <-> VIFe2+ + IVSi4+
Illite y = -0.5x
0.6 0.0
2.0 2.2 2.4 2.6 2.8 3.0 2.2 2.4 2.6 2.8 3.0
Total Al (apfu) Total Al (apfu)

C D Toward
Celadonite Aluminoceladonite Muscovite
2.0 1.0

1.9
K/(K+Na+Ca)

0.9
K+ <-> Na+
Alvi (apfu)

1.8
In c
re a
1.7 s in
gT
s ch 0.8
e rm
ak
1.6 su b
sti
tu t
io n
Paragonite
1.5 0.7
0.00 0.05 0.10 0.15 0.20 0.25 2.0 2.2 2.4 2.6 2.8 3.0
Fe (apfu) Total Al (apfu)

Early Green Phyllic Alteration (EGPA)

Late White Phyllic Alteration (LWPA)
Fig. 12. Compositional variations in major elements between the early green phyllic alteration and the late white phyllic
alteration from individual microprobe analyses. A) Total Al vs. K + Na + Ca diagram indicating Tschermak and illitic substitu-
tion. B) Total Al vs. Fe + Mg + Mn diagram. White micas from both alteration styles display significant scatter; however, most
of the data points lie between the Tschermak and the VIFe3+ ↔ VIAl3+ substitution lines, suggesting a contribution of Fe2+ and
Fe3+ to measured FeTOT + Mg + Mn contents. C) Fe vs. Alvi diagram marking the main compositional difference between
the two phyllic alteration styles. D) Total Al vs. K/(K + Na + Ca) diagram showing limited K+ ↔ Na+ substitution. Arrows
represent compositional vectors for main substitution mechanism, and dashed lines represent the equations derived by least-
squares linear regression. apfu = atoms per formula unit.

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 1286 URIBE-MOGOLLON AND MAHER

aluminoceladonites associated with the late white phyllic style
shows a spatial relationship with distal zones of the Copper Cliff
system (e.g., hole CC17), in contrast to samples of the early
green style where the spatial relationship is not clearly evident.
Based on the microprobe analyses, muscovitic composition was
only observed in white micas from the late phyllic style, consti-
tuting 16% of that population.
In Figure 12B, most of the data points plot between the
dashed lines representing the ideal Tschermak substitution
line and the VIFe3+ ↔ VIAl3+ substitution line within the total
aluminum versus octahedral cation diagram. This relationship
suggests variable amounts of Fe2+ and Fe3+ in the structure
of white micas, as proposed by Cohen (2011). In the absence
of direct measurement, the unequivocal distinction between
Fe2+ and Fe3+ is impossible from the EMPA data alone (Bous-
and V exist between the early and late phyllic alteration styles.
By contrast, ANOVA suggests no significant difference (p >
0.05) in the concentrations of Ba, Ce, Co, Cr, Cu, La, Li, Mn,
P, Sr, Tl, W, Y, and Zn.
Discussion
Timing of the phyllic alteration
Considering the complexity of the argon age spectra, apparent
ages recorded by the final heating steps and the isochron ages
are very consistent with the other geochronological constraints.
The weighted mean ages of 49.55 ± 0.17, 49.29 ± 0.18, and
49.79 ± 0.11 Ma for the early green and the late white phyllic
alteration samples are analytically indistinguishable from the
40Ar/39Ar alunite age and the Re-Os ages. Sample CC17-1093

quet et al., 2002). However, an estimate of the Fe2+/Fe3+ ratio from the late white phyllic alteration has a very small fraction
can be made according to the relative position of the points of the spectrum that yields a weighted mean age of 50.02 ±
between these two substitution lines. Therefore, points follow- 0.22 Ma and at 2σ uncertainty is equal to the other weighted
ing the Tschermak substitution line will have a slope of –0.5, mean ages (Fig. 9D). The consistency of the weighted mean
and Fe3+/(FeTOT + Mg + Mn) = 0; conversely, points following ages, isochron ages, and other geochronological constraints
the VIFe3+ ↔ VIAl3+ substitution line will have a slope of –1,
and Fe3+/(FeTOT + Mg + Mn) = 1 (Cohen, 2011). White micas 10000
from both alteration styles display significant scatter in these
compositional parameters; however, using a least-squares
1000
regression method, white micas from the early green phyllic
alteration are represented by the equation y = –0.7025x (R2 =
0.36). As a result, if the slope is –0.7025, then Fe3+/(FeTOT  + 100
Mg + Mn) = 0.405, which indicates ~40.5% contribution of
ppm

Fe3+ to measured FeTOT + Mg + Mn contents. In the case

of the late phyllic style, white micas are represented by the 10
equation y = –0.4957x (R2 = 0.33), derived by least-squares
linear regression. The slope of this equation is higher than
1
–0.5, indicating 0% contribution of Fe3+ to measured FeTOT
+ Mg + Mn contents. Evidence for the VIFe3+ ↔ VIAl3+ sub- B V Rb Cl
stitution in white micas is supported by the ANOVA analysis, 0.1
which shows no significant difference in the concentrations
of silicon between both phyllic alteration styles. Therefore, 100
differences in the iron content (Fig. 12C) must be primarily
associated with the contribution of Fe3+. Consequently, white
micas from the early green phyllic alteration are differenti- 10
ated from those of the late phyllic alteration by the relatively
higher iron content, which in turn reflects greater substitu-
tion for aluminum. In Figure 12D, the total aluminum versus
ppm

1
K/(K + Na + Ca) diagram shows no significant difference in
Na+ ↔ K+ substitution in the interlayer cation site for the two
alteration types, except for three samples from the early green
0.1
phyllic alteration overprinted by kaolinite.
Trace element variation: Trace element composition of
white micas was determined by LA-ICP-MS. Representative Cd Cs Sc Sn
analytical results are shown in Table 2, and reproducibility and 0.01
detection limits are given in Table A3 of the Digital Appen- Early Green Phyllic Alteration (EGPA)
dix. In order to monitor the effect of mineral inclusions on
the analytical signal, Ca, Mg, and Ti were also analyzed, and Late White Phyllic Alteration (LWPA)
contaminated signals were not used. Compositional variations Fig. 13. Compositional variations in trace elements for white micas from the
of analyzed trace elements for white micas are shown in Fig- early and late phyllic alteration styles. Analysis of variance (one-way ANOVA)
ure 13. A one-way ANOVA statistical procedure at 95% con- at a 95% confidence level demonstrates significant differences in the content
of B, V, Rb, Cl, Cd, Cs, Sc, and Sn. Symbols represent the middle 50% of
fidence level was used to test the variations in trace element the data (box), the mean value (cross), and the median (horizontal line), and
concentrations between the two styles of phyllic alteration the whiskers are the 5 and 95% values; black dots represent outliers. The
(see Digital App. Table A4). In general, significant variations numbers of analytical points for the early and late phyllic alteration are 48
(p < 0.05) in the concentrations of B, Cd, Cl, Cs, Rb, Sc, Sn, and 31, respectively.

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 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1287

Table 2. Representative LA-ICP-MS Analyses of White Micas at Copper Cliff

  CC10- CC10- CC10- CC10- CC13- CC5- CC13- CC13- CC7- CC13- CC13-
Sample 955-1 1074-1 1156-1 1231-1 1078-1 748-1 410-1 361-1 332-1 1412-1 203-1

Distance to
deposit center (m)
0 121 199 273 351 432 522 565 580 620 710

Alteration EGPA EGPA EGPA EGPA EGPA EGPA EGPA EGPA EGPA EGPA EGPA

Li 5.2 3.1 2.5 BDL 6.6 5.7 BDL 2.4 6.3 34.4 BDL
B 25.7 10.1 BDL BDL 27.4 12 BDL 54.4 19.8 34 42
P 209 427 194 27 134 49 165 270 355 343 793
Cl 497 277 312 259 505 488 368 747 610 528 490
Sc 7.6 8.9 6.6 0.5 8.1 1.8 0.6 10.6 1.9 7.5 8.9
V 36.6 32.5 48 1.1 52.2 75.6 4.4 62.4 15.9 79 88.3
Cr 48 26.6 16.4 BDL 29.6 107 2.4 48.3 10.3 184.3 95
Mn 30.9 19.2 7.4 11.5 16.4 4.6 12.2 35 83.5 151.8 19
Co 1.25 0.1 0.68 0.07 3.05 1.43 0.37 0.67 6.03 4.25 0.45
Cu 131.9 71.1 11.1 35.8 37.1 50.8 11.7 29.7 40.7 68.9 15.7
Zn 45 26.8 12.6 20.5 25.9 103.6 70.2 122 156 380 126
Se BDL BDL BDL BDL BDL BDL BDL BDL BDL 3.5 BDL
Rb 166 55 69.8 2.2 183.5 9.5 6.5 195.1 161.6 89.8 271.9
Sr 4 83 5 1 11 2 210 32 174 215 16
Y 2.41 6.3 64 0.06 4.73 2.15 0.75 0.18 0.83 10.46 0.58
Cd 0.67 0.24 1.13 0.16 3 1.64 0.16 1.21 0.29 3.44 2.21
Sn 3.81 1.38 4.84 0.17 8.13 9.6 0.27 6.23 1.51 9.02 5.25
Cs 2.15 0.49 0.39 0.07 3.91 0.07 0.22 4.37 2.59 5.99 3.42
Ba 226 435 205 10 124 7 41 276 980 560 360
La 0.06 149 1.7 0.23 4.45 0.06 1.21 0.64 7.8 40.8 0.57
Ce 0.06 270 4.4 0.52 4.1 0.16 2.31 1.66 12.3 55.1 0.96
W 1.68 0.21 1.7 0.26 4.81 0.29 0.11 5.56 0.68 9.87 1.31
Tl 5.08 1.03 1.58 0.07 3.98 0.38 0.27 7.28 6.56 1.74 12.5

CC2- CC8- CC13- CC9- CC11- CC5- CC13- CC8- CC8- CC4- CC17- CC17-
Sample 72-1 1487-1 1985-1 1063-1 1156-1 355-1 1514-1 758-1 1545-1 94-1 1043-1 610-1

Distance to
deposit
center (m) 841 942 1,170 495 527 665 715 830 974 986 1,336 1,358

Alteration EGPA EGPA EGPA LWPA LWPA LWPA LWPA LWPA LWPA LWPA LWPA LWPA

Li 3.7 8.4 1.3 BDL 2.8 1.6 8.7 3.3 4 BDL 2.1 13.2
B 38.1 42.6 BDL 49 23.4 37.4 20.7 52.6 37 65.4 66.2 60.3
P 227 307 1,020 313 153 312 161 263 93 2,710 45 1,129
Cl 484 479 199 401 937 512 380 481 508 689 440 759
Sc 7.9 7.2 0.6 12.6 9.2 10 11 12.9 9.6 9.3 9.4 15
V 100.4 51.8 BDL 117.3 99.7 111.7 131.3 99.1 91.1 148.7 111.3 144.6
Cr 221.2 15 2.2 108.9 6.3 41 57.8 6.7 46.5 24.2 3.4 22
Mn 29.2 32.8 332 1.9 3.1 5 8.9 45.8 5.5 16.8 12.8 324
Co 2.43 0.77 0.77 1.27 0.28 0.44 2.88 3.74 0.69 0.95 0.22 0.8
Cu 28.8 6.1 3.3 65.7 8.2 21.5 21.9 31.1 11.4 7.4 55.2 36.3
Zn 96 47.8 11.5 75.8 11.1 28.1 44.3 79.5 38.1 27.3 183.2 200
Se BDL BDL BDL 2 BDL BDL BDL BDL BDL 3.91 BDL BDL
Rb 222.9 167.3 140 134.9 182.1 154.7 183.7 224.2 210.5 167 238.5 191.6
Sr 41 110 333 10 36 10 33 151 591 2,750 29 318
Y 0.16 0.27 2.05 0.42 2.66 0.14 0.13 2.13 4.53 1.62 0.12 4.49
Cd 2.73 2.1 0.28 0.32 3.39 3.09 1.9 0.33 2.48 2.73 1.42 0.38
Sn 15.01 14.52 0.12 1.81 7.82 18.88 11.73 1.95 17.29 18.39 5.08 1.7
Cs 3.36 2.32 0.78 0.62 1.22 1.58 1.15 2.75 1.16 3.16 13.43 6.75
Ba 290 223 2,890 13 2,300 397 1,246 2,892 112 788 226 9,700
La 0.19 0.32 4.72 0.05 1.43 0.04 0.11 34 14 670 0.08 12.7
Ce 0.43 0.51 9.4 0.18 3.62 0.13 0.25 46 36.3 1,380 0.09 21.2
W 2.16 5.14 BDL 0.06 1.23 1.12 5.03 0.3 5.75 0.43 0.05 0.29
Tl 8.2 2.48 1.85 2.35 5.63 12.5 2.06 2.83 3.4 7.94 4.06 1.81

Note: All concentrations reported in parts per million (ppm)

Abbreviations: BDL = below detection limit, EGPA = early green phyllic alteration, LA-ICP-MS = laser ablation-inductively coupled plasma-mass spec-
trometry, LWPA = late white phyllic alteration

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 1288 URIBE-MOGOLLON AND MAHER

may provide important limits for interpretation of this form

of white mica age spectra. The age spectra and assigned A
weighted mean ages by themselves would have ambiguous 2.0
meaning, especially due to potential 39Ar recoil impacts; how-
ever, the consistency between all geochronological methods R2 =0.47
strongly argues that utilizing the final heating steps for spectra 1.9
of this nature can yield accurate alteration ages. Finally, the
white mica argon results indicate that the early green and late

Alvi (apfu)
1.8
white phyllic alteration formed within the analytical uncer-
tainty of the argon ages, thus being within no more than a few
Inc
hundred thousand years of each other. 1.7 re a s
in g
T sc
her
Variation in the Al-OH band wavelength with m ak
su b
the major element geochemical data 1.6 stitu
tio n
The compositional variation of micas from the early and late
phyllic alteration styles is reflected in the SWIR data (Fig. 1.5
14). Figure 14A shows an inverse relationship between the 2196 2200 2204 2208 2212
amount of aluminum in the octahedral site and the location of W avelength (nm)
the Al-OH combination band center. The range of the Al-OH B
band center wavelength from 2,198 to 2,206 nm corresponds
to micas with calculated high octahedral aluminum (VIAl), 0.25
generally from 1.7 to 1.9 apfu, associated with the late phyl-
io n
lic alteration. Moreover, the range of the Al-OH band center i tu t
0.20
su b st
wavelength from 2,206 to 2,210 nm corresponds to white micas ak
rm
with low VIAl, typically between 1.5 and 1.8 apfu, characteristic s c he
F e (a pfu)

of the early phyllic alteration. Similar ranges for the location of 0.15 in gT
r eas
the Al-OH combination band center and Al content in the octa- Inc
hedral site of white micas in porphyry systems were reported in 0.10
recent studies (Swayze et al., 2014; Graham et al., 2018).
The relationship between the iron content in the octahe-
2
dral site and the Al-OH band center wavelength is shown 0.05 R = 0.63
in Figure 14B. Long-wavelength white micas in the range
of 2,206 to 2,210 nm have high iron (0.09–0.2 apfu) values,
0.00
whereas short-wavelength white micas in the range of 2,198 to 2196 2200 2204 2208 2212
2,206 nm correspond to low iron (0.02–0.09 apfu) values. This W avelength (nm )
variation observed in the Al-OH band center wavelength of
the white micas appears to be mainly attributed to the Tscher-
mak substitution VIAl3+ + IVAl3+ ↔ VIFe2+ + IVSi4+. Therefore, Early Green Phyllic Alteration (EGPA)
the Al-OH band center wavelength and related cation com-
Late White Phyllic Alteration (LWPA)
position (e.g., FeTOT and VIAl) can be used to differentiate the
main phyllic events at the Copper Cliff porphyry Cu system. Fig. 14. Single microprobe analysis and associated position of the Al-OH
It is noteworthy that where magnesium concentrations are combination band center determined from the same sample billet. A) Cal-
culated Alvi and the Al-OH band center with an inverse relationship. B) Iron
higher than iron in both alteration styles, the relationship with content and Al-OH band center showing the positive relationship. Arrows
the Al-OH band center wavelength is not clearly indicated. represent compositional vectors for Tschermak substitution and dashed lines
The SWIR spectral absorption features located around represent least-squares linear regressions. apfu = atoms per formula unit.
715, 890 and 1,100 nm in samples of white micas from the
early green phyllic alteration are interpreted to be the result
of electronic processes, such as the charge transfer between compositions based on the microprobe data (Fig. 12A).
Fe2+ and Fe3+, or crystal field effects by unfilled electron
shells of transitional metals (Burns, 1993). In addition, the Implications of trace element geochemistry
absorption feature near 2,250 nm seems to be related to the The overall difference in trace element content in white micas
presence of Mg2+ and/or Fe3+ in the octahedral site (Scott and of both phyllic alteration styles is shown in Figure 15. Scan-
Yang, 1997). Swayze et al. (2018) noted that the development dium and vanadium concentrations in white micas from the
of a shoulder near 2,250 nm is likely attributed to MgFe3+ late phyllic alteration are notably higher than those from the
and MgAl cation pairs bonded to OH groups in the structure early green phyllic style. Concentrations of scandium in the
of white micas. Likewise, the intensity of the shoulder corre- early green phyllic style range from 0.4 to 12.9 ppm, whereas
lates with the decrease of aluminum in the octahedral site and in the late phyllic alteration concentrations range between 8.2
the shifting to longer wavelengths of the 2,200 nm absorption and 20.7 ppm. Vanadium varies from 0.7 to 100.4 ppm in the
feature (Swayze et al., 2014). The water absorption feature early phyllic style and from 81.7 to 204.2 ppm in the late phyl-
at 1,900 nm correlates well with samples containing illitic lic alteration.

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 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1289
250
R2 = 0 .6 8
200
150
V (ppm)
100
50
0 micas from early alteration presents vanadium concentrations
0 5 10 15
Sc (ppm)
Early Green Phyllic Alteration (EGPA)
Late White Phyllic Alteration (LWPA)
Fig. 15. Plot of scandium versus vanadium concentrations from laser ablation-
inductively coupled plasma-mass spectrometry spot analyses in white micas.
White micas from the late white phyllic alteration show higher concentrations
of scandium and vanadium than those from the early green phyllic alteration.
Dashed line represents least-squares linear regression of all data.
Scandium and vanadium can be easily accommodated into the
octahedral site of white micas. Scandium, as a 3+ cation (Sc3+),
has a similar atomic radius in the sixfold coordination (0.75 Å)
to Fe2+ (0.78 Å). Likewise, vanadium as a 3+ cation (V3+) has an
atomic radius (0.64 Å) almost identical to that of Fe3+ (0.65 Å).
Previous studies have documented that under strongly oxidized
magmatic conditions, vanadium is more common as V4+ and V5+
rather than V3+ (Schuiling and Feenstra, 1980; Loucks, 2014).
Schuiling and Feenstra (1980) also showed that hematite in
magnetite-hematite pairs concentrates more vanadium than
magnetite alone (Lund, 2009). In the early green phyllic phase
at Copper Cliff, the association of specular hematite and anhy-
drite is indicative of oxidized conditions of porphyry-derived
fluids. Therefore, we suggest that in this alteration stage vana-
dium will most likely behave as V4+ and will be concentrated in
the associated specular hematite rather than the white micas,
where the latter averages an estimated 40.5% contribution of
Fe3+ to measured FeTOT + Mg + Mn contents (Fig. 12B). In the
same way, the low content of scandium in white micas from the
early green phyllic phase may be caused by the incorporation
of this element into specular hematite (Schuiling and Feenstra,
1980). At this point, this problem requires detailed studies,
including major and trace element geochemistry in associated
specular hematite and Mossbauer determination of Fe2+/Fe3+
in the white micas.
The distinctive shift from the presence of specular hematite
and anhydrite in white micas from the early phyllic alteration
to the absence of these minerals in the late phyllic style sug-
gests a change to more reduced conditions over time. The
more reduced conditions during the late phyllic alteration
event could explain the concomitantly higher concentrations of
vanadium and scandium in these late white micas. Under low
oxygen fugacity, vanadium and scandium behave as a 3+ cation
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(Mallmann and O’Neill, 2013; S. Halley, unpub. report, 2016),
and both may substitute for Fe3+ into the white mica’s structure.
The above-mentioned hypothesis is supported by the fact
that only plagioclase phenocrysts intensely affected by white
mica were analyzed in the late phyllic alteration, whereas the
influence of the precursor mineral phase could not be ascer-
tained in the early green phyllic alteration due to the pervasive
and destructive style of the event. Presumably at least some of
the white micas analyzed from the early green phyllic alteration
replaced mafic mineral phases, therefore vanadium concentra-
tions should be higher in these than in white micas from the
late phyllic style, assuming a protolith control in the metal con-
tent of the white micas; however, only a fraction of the white
20 that exceed the minimum concentrations measured in late
white phyllic alteration micas (Fig. 15). This suggests that the
fluids responsible for alteration during the early event were too
oxidized to preserve vanadium in the relatively reduced 3+ state
to be incorporated into white micas. Therefore, chemical varia-
tions in major and trace element concentrations between white
micas from the early green and late white phyllic alterations can
be explained by different fluid conditions.
Previous studies have suggested that the phyllic alteration
is the result of the late-stage ingress of oxidized meteoric
fluids into the magmatic-hydrothermal system (e.g., Taylor,
1974; Gustafson and Hunt, 1975; Sheets et al., 1996; Dilles
et al., 2000); however, as has been observed in this study, the
early green phyllic alteration was formed by oxidized fluids,
and based on the contemporary paragenetic relationship to
the potassic alteration, it is a product of magmatic rather than
meteoric fluids. Harris and Golding (2002) have reported iso-
topic evidence from white micas that supports a magmatic
origin for at least some phyllic alteration at the Endeavour 26
North (E26N) porphyry Cu-Au deposit in Australia.
Spatial variations in white mica composition
Trace element trends in white mica from other deposits: Previ-
ous studies have documented the compositional variation in
white micas at different distances from the mineralized center
in porphyry systems, e.g., Ann-Mason porphyry Cu deposit in
Nevada, United States (Cohen, 2011), and Highland Valley
porphyry Cu-Mo deposit in British Columbia, Canada (Alva
Jimenez, 2011). At the Ann-Mason system, vertical trans-
verses show that Tl content in white micas increases with
distance out from the porphyry center, whereas W and Sn
concentrations increase toward the center. At the Highland
Valley system, lateral transverses show that in addition to Tl,
trace elements in white micas, including B, Co, Cs, Mn, and
Zn, generally increase in concentration with distance from the
hydrothermal center. In contrast, other trace elements such
as Li, Sn, Sr, Ti, and V show decreased concentrations with
increasing distance. Cohen (2011) and Alva Jimenez (2011)
argued that the observed systematic trace element patterns
are mainly temperature controlled, although no thermal gra-
dients were constrained in either of those studies to test such
a hypothesis. The suggested thermal control of element sub-
stitution in white mica requires further investigation; how-
ever, experimental studies have highlighted similar effects on
the behavior of titanium content in white mica by analogy to
biotite, which tends to increase with temperature (Auzanneau
 1290 URIBE-MOGOLLON AND MAHER

et al., 2010; Wu and Chen, 2015). In the same way, thermo-
dynamic studies in porphyry systems have found significant
concentrations of As, Cu, Sc, Sn, Sr, Ti, V, and Zn in the lattice
of alteration minerals such as chlorite and epidote, which for
those minerals can be correlated to variations in temperature
of the hydrothermal fluids according to chlorite geothermom-
etry (Wilkinson et al., 2015; Xiao et al., 2017).
White mica proximitor
Following the protocol utilized by Wilkinson et al. (2015),
element concentrations in white micas at Copper Cliff were
plotted as a function of radial distance from the center of the
system in order to identify the spatial variations. Point-based
element concentrations instead of sample-average data were
used in this analysis for a given distance. Suggested trends
were evaluated separately in each phyllic alteration style
using one-way ANOVA, and only elements with significant
differences (p < 0.05) are discussed below (see Digital App.
Tables A5, A6). In general, white micas from the early and
late phyllic alterations are enriched in Cu proximal to the
center of the deposit (hole CC10) compared with those at
the margin (Fig. 16A). By contrast, in both phyllic altera-
tion styles Zn occurs in higher concentrations at the mar-
gins than at the deposit center (Fig. 16B). Overall increasing

A B
1000 1000

100 100
Cu (ppm)

Zn (ppm)

10 10

1 1
0 500 1000 1500 0 500 1000 1500
Distance to system center (m ) Distance to system center (m )

C D
10000 100

1000
Sr (ppm)

B (ppm)

100

10

1 10
0 500 1000 1500 500 1000 1500
Distance to system center (m ) Distance to system center (m )

Early Green Phyllic Alteration (EGPA)

Late White Phyllic Alteration (LWPA)
Fig. 16. Trace element concentrations in white micas from both early and late phyllic alteration styles determined by laser
ablation-inductively coupled plasma-mass spectrometry spot analyses as a function of radial distance from the Copper Cliff
center. The limit of the imprint of the early green phyllic alteration (EGPA) is within 710 m, therefore samples located beyond
this distance from the deposit center are noninformative. In a similar way, the limit of the expression of the late white phyllic
alteration (LWPA) is 1,300 m from the deposit center. A) Copper shows relative enrichment proximal to the mineralized cen-
ter. B) Zinc shows depletion proximal to the center and enrichment at the margins. C) Strontium concentrations increase with
distance from the deposit center only in EGPA samples. D) Boron concentrations increase with distance from the deposit
center only in LWPA samples.

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 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1291

concentrations of Sr from the center to the margins of the
deposit exist exclusively in the early green phyllic style (Fig.
16C). Boron shows a similar trend but only for the late white
phyllic alteration (Fig. 16D). With the exception of stron-
tium, these spatial variations relative to the porphyry center
are similar to those displayed at the Highland Valley system
(Alva Jimenez, 2011), which could imply that temperature is
also one of the controlling factors affecting the composition
of white micas at Copper Cliff.
The spatial variations of trace elements in white mica can be
amplified for exploration purposes by comparing the ratio of
elements with decreasing outward patterns to those showing
increasing outward patterns (Wilkinson et al., 2015). Ratios
were plotted exponentially as a function of radial distance out
from the center of the porphyry system (Fig. 17). According
to the data, the Cu/Zn ratio shows the best exponential fit
parameter (R2 = 0.8) in both phyllic alteration styles. In the
early green phyllic alteration, the exponential decay of the Cu/
Zn ratio as a function of distance from the deposit center is
described by the equation y = 4.076e–0.005x. This decay func-
tion is only valid to distances out to 710 m, which is the point
where the Cu/Zn ratio stabilizes, and it is considered the limit
of the imprint or preservation of the early phyllic alteration
event. In the case of the late phyllic alteration, the exponential
decay has the form of y = 1.7857e–0.002x to distances between
500 and 1,300 m.
Distance to the porphyry center can be estimated by rear-
ranging the exponential regression equation to x = (ln [R/a])/b,
where x is the distance in meters to the porphyry center, R is
the element ratio, and a and b are the exponential fit param-
eters (Wilkinson et al., 2015). Thus, in the early green phyllic
alteration the distance to the deposit center can be described
by the following equation for samples located within a 710-m
radius from the center of the porphyry system: distance (x) =

A B
1000 1000

100 100

10 10
Cu/Zn
Cu/Zn

1 1
R2 =0.89
0.1 0.1 Y = 4.076e-0.005x
ln {Cu ⁄ 4 .076 Zn }
Distance =
0→710m − 0.005
0.01 0.01
0 500 1000 1500 0 250 500 750
Distance to system center (m) Distance to system center (m)

C
1000

100

Early Green Phyllic Alteration (EGPA)

10
Cu/Zn

Late White Phyllic Alteration (LWPA)

1 Whole-Rock data
Y = 1.7857e-0.002x
0.1 R2 =0.80
ln {Cu ⁄ 1.7857 Zn}
Distance =
500 →1300m − 0.002
0.01
500 750 1000 1250 1500
Distance to system center (m)
Fig. 17. Trace element concentration ratios from individual laser ablation-inductively coupled plasma-mass spectrometry spot
analyses in white micas from both phyllic alteration styles as a function of radial distance from the Copper Cliff center. A)
Cu/Zn ratio. Note the whole-rock ratio data for comparison. Whole-rock data comes from assay intervals from which the drill
core samples were taken. B) Cu/Zn ratio for samples with early green phyllic alteration. C) Cu/Zn ratio for samples with late
white phyllic alteration. Dashed line represents least-squares linear regression.

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 1292 URIBE-MOGOLLON AND MAHER
ln (Cu/4.076Zn)/(–0.005). In the same way, the distance equa-
tion for the late phyllic style is as follows for samples located
between 500 and 1,300 m from the deposit center: distance
(x) = ln (Cu/1.7857Zn)/(–0.002).
To test the equation, estimated distances were calculated
applying the Cu/Zn ratio and compared against the actual dis-
tances to the center of the system in order to evaluate the
accuracy of the method (Fig. 18). The plot demonstrates
that the Cu/Zn ratio for samples showing early green phyllic
alteration within a 710-m radius of the deposit center pre-
dicted the distance to center within ±50 m radius error. Out-
side the 710-m radius, where the gradient of the Cu/Zn ratio
versus distance relationship stabilizes, distances to the center
are underestimated within approximately 400 m. In the same
way, the Cu/Zn ratio for samples showing late phyllic altera-
tion within a radius between 500 and 1,300 m of the deposit
center underestimate distances to the center by about 200 m.
A decreasing-outward pattern with distance from the porphyry
1500
Dista n ce to system cen ter (m )
1250
1000
750
500
250
0 This suggests a potential advantage in using the white mica
B tances to a hydrothermal center.
1500
Distance to system center (m )
1250
1000
750
500
250
0 center seems to be associated with a decrease of the location
Real distance
Estimated distance
Fig. 18. Comparison of actual distances versus estimated distances based on
the Cu/Zn proximitor equation. A) The Cu/Zn ratio for samples with early
green phyllic alteration located within a 710-m radius of the deposit center
predicts the distance to center within ±50 m radius error. Beyond the 710-m
radius, distances to center are underestimated within approximately 400 m.
B) The Cu/Zn ratio for samples with late white phyllic alteration located
within a radius between 500 and 1,300 m of the deposit center underesti-
mates distances to center within ±200 m radius error.
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One of the implicit assumptions to the application of this
method is that the fluids emanated from a single hydrother-
mal center; however, the potential proximity provided by
the equation is unclear if multiple fluid centers are present,
and this concern will be treated in a future publication. In
the same way, the protolith control over white mica compo-
sitions needs to be considered, since variations in trace ele-
ment concentrations in micas have been reported in some
systems, depending upon the original protolith mineral that
was replaced and the host rock (Alva Jimenez, 2011; Jin et
al., 2018). However, for the Copper Cliff system there is no
evidence of protolith-controlled variation, probably due to the
relative homogeneous composition of the host porphyries 1A
and 1B and the volumes of fluids involved.
Comparison with whole-rock data
Comparison of Cu/Zn ratio in white micas to whole-rock data
from the assays indicates that the Cu/Zn ratios for the whole-
rock assays are significantly higher, but they follow the same
center as white mica analyses (Fig. 17A). This suggests that
the Cu/Zn footprint could be defined by the whole-rock geo-
chemistry; however, since the sample media (mica vs. rock)
differ, contributions from white micas to rock chemistry were
not determined. In a general sense, it is possible that the Cu/
Zn ratio from whole-rock analyses will be modified during
supergene weathering and/or subsequent alteration events
and so may not be effective in all systems. For example, in
phyllically altered rocks with advanced argillic alteration over-
print, the whole-rock Cu/Zn ratio may not indicate distance to
the center of the system. In contrast, the individual phyllosili-
cates may be better preserved through overprinting alteration
events and thus be more diagnostic than the whole-rock ratio.
proximitor method over whole-rock analyses to estimate dis-
Variation in the Al-OH band wavelength with
the Cu/Zn ratio
The Cu/Zn ratio in white micas from the early and late phyllic
alteration styles was compared with the wavelength position
of the Al-OH band center in order to provide a key guide for
exploration (Fig. 19). In samples from the early green phyl-
lic alteration, the relationship between the Cu/Zn ratio and
the wavelength position of the Al-OH band center in white
micas is nonexistent or not clearly indicated (Fig. 19A).
However, in samples from the late phyllic alteration within
a radius between 500 and 1,300 m, the exponential decay of
the Cu/Zn ratio as a function of distance from the deposit
of the Al-OH combination band center (Fig. 19B). High Cu/
Zn ratios predominate in white micas with short Al-OH band
centers having wavelengths in the range of 2,198 to 2,202
nm. By contrast, white micas with long Al-OH band centers
having wavelengths in the range of 2,202 to 2,208 nm pres-
ent low Cu/Zn ratios. Therefore, the variation of the white
mica Al-OH band center associated with changes in the Cu/
Zn ratio represents a powerful tool for exploration that may
provide a sensitive indicator of distance to the center of the
system.
 COPPER CLIFF PORPHYRY Cu DEPOSIT, MONTANA, USA 1293

10
A
R2 = 0.89

C u/Zn
1

0.1
0 250 500 750
Distance to system center (m )

1
B
R2=0.80
C u/Zn

0.1
500 750 1000 1250 1500
Distance to system center (m )

White mica wavelength position (nm)

2,198 – 2,200 nm 2,202 – 2,204 nm 2,206 – 2,208 nm

2,200 – 2,202 nm 2,204 – 2,206 nm 2,208 – 2,210 nm
Fig. 19. Variation in Cu/Zn from laser ablation-inductively coupled plasma-mass spectrometry spot analyses relative to dis-
tance, plotted by Al-OH band centers. A) Samples from the early green phyllic alteration show no significant variation in
Al-OH band center. B) Samples from the late phyllic alteration within a radius between 500 and 1,300 m show an exponential
decay of the Cu/Zn ratio as a function of distance from the deposit center and seem to be associated with a decrease of the
position of the Al-OH combination band center. Dashed lines represent least-squares linear regressions.

Conclusions
Variations of the mineral assemblage and the Fe, V, and Sc
content in white micas at the Copper Cliff system suggest dif-
ferent oxidation conditions prevailed between the formation
of the early green phyllic alteration and the late white phyllic
alteration. In general, white mica from the early green phyllic
alteration style is Fe rich and V and Sc poor, formed by oxidized
magmatic fluids more or less contemporary with the potassic
alteration. In contrast, the Fe-poor, and V- and Sc-rich white
mica from the late phyllic event was formed by more reduced
fluids. The two distinctive phyllic alteration styles can also be
discriminated based on the Al-OH band center wavelength,
varying between 2,197 and 2,206 nm for the late white phyllic
phase and between 2,206 and 2,210 nm for the early green
phyllic style. Geochemistry of white micas shows clear pat-
terns in the trace element compositions in relationship with
distance from the hydrothermal center, which we suggest is at
least partly a function of crystallization temperature. Copper
concentrations decrease with distance from the deposit cen-
ter, in contrast to B, Sr, and Zn that show an exponential con-
centration increase with distance from the porphyry center.
In a manner analogous to the chlorite proximitor of Wilkinson
et al. (2015), application of elemental ratios (e.g., Cu/Zn) in
white mica compositions can provide an indicator of distance
to the heat/fluid source within approximately 1,300 m radial

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 1294 URIBE-MOGOLLON AND MAHER
distance in the case of late phyllic alteration. The Cu/Zn ratio
in white micas from late phyllic alteration appears to correlate
to the position of the Al-OH band center wavelength (Fig.
19B). Since there are different vectors associated with each
phyllic alteration type, we believe that it is necessary to dis-
criminate between different phyllic alteration events prior to
interpreting geochemical vectors based on mica chemistry
from alteration assemblages in porphyry systems.
Acknowledgments
This work was supported through the grant no. 646 of COL-
CIENCIAS (Colombia), the Economic Geology research
group of New Mexico Tech, and Kennecott Exploration Com-
pany. Special thanks are extended to Clinton Roberts, Russ
Franklin, and Russ Eley for facilitating the field work, pro-
viding access to drill hole samples, and providing data from
internal Kennecott Exploration Company reports. Thanks
to Dr. Matt Heizler, from the New Mexico Geochronology
Research Laboratory, for his help generating and interpreting
the 40Ar/39Ar geochronology data.
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Kierran Maher completed his Ph.D. degree in
geology at Washington State University followed
by a postdoc in copper isotope fractionation at
Macquarie University, Australia. Since 1996, Dr.
Maher has periodically worked in mineral explora-
tion on copper porphyry, copper skarn, and Ni-Cu
magmatic sulfide systems for various companies in
North and South America. He currently teaches mineralogy, mineral depos-
its, and exploration geochemistry classes in the Earth and Environmental Sci-
ence Department at New Mexico Institute of Mining and Technology, New
Mexico, USA, oversees graduate research in mineral deposits, and presents
short courses on hydrothermal alteration in South America. His research
interests lie in hydrothermal alteration mineralogy and geochemistry.
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