SOCIETY OF ECONOMIC GEOLOGISTS

INTERNATIONAL EXCHANGE LECTURE - JUNE 1994

High Sulfidation and Low Sulfidation Porphyry Copper/Skarn Systems: Characteristics,

Continua, and Causes

Marco T. Einaudi, Stanford University Stanford, California, U.S.A.

https://pangea.stanford.edu/research/ODEX/marco-hilosulf.html

In the past decade, multi-disciplinary research on active and fossil hydrothermal systems in
volcano-plutonic arcs has resulted in important new information on the physical and chemical
evolution of hydrothermal fluids of diverse origin, on the sources of metals, sulfur and other
dissolved constituents, and on the possible genetic transitions between different ore-forming
environments. Among the most studied magma- hydrothermal systems are those linked to felsic
magmatism, whose products extend from plutonic porphyry-Cu deposits to volcanic epithermal-
Au deposits. In-between these end members can be skarns or massive sulfide replacement
bodies and veins of both base- and precious-metals. Here I focus on transitions between ore
types in porphyry copper systems and use the sulfidation state of hydrothermal fluids as a
framework. I adopt the sulfidation state as a means of classification of ore-forming environments
because this variable spans all deposit types and is independent of host rocks, metals
contained, and textures exhibited (in contrast with terms such as "acid-sulfate" which is
restricted to quartzo- feldspathic host rocks, or "epithermal" which is restricted to one class of
deposit).

Sulfidation State.

McKinstry (1959, 1963) and Barton (1970) applied the terms "sulfur content" and "sulfidation
state", respectively, to denote the relative values of the chemical potential of sulfur implied by
sulfide mineral assemblages in ore deposits. Both authors noted the general tendancy for
sulfidation state to increase as unbuffered hydrothermal solutions evolve from high to low
temperatures in base- metal veins associated with felsic igneous rocks. The concept of
sulfidation state was put on a firm theoretical and experimental base by Skinner and Barton
(1967, 1979) and applied to base-metal veins by Meyer and Hemley (1967).

The sulfidation state of hydrothermal fluids can be classified on a continuous scale on the basis
of key sulfidation reactions, as defined in Table 1 below (based on Skinner and Barton, 1979).
In bold letters are minerals or assemblages that span only two defined sulfidation states; in italic
bold are minerals or mineral assemblages that occupy only one defined state.

Only a few minerals or mineral assemblages are diagnostic of a given sulfidation state. For
example, although covellite is diagnostic of very high sulfidation states, enargite is less
diagnostic, being stable from upper intermediate, through high, and very high sulfidation states.
Because of the chemical links between sulfidation, oxidation, and ionization states of
hydrothermal fluids (Meyer and Hemley, 1967), covellite would be expected to be associated
with acid-sulfate fluids and advanced argillic alteration containing alunite. Enargite, on the other

hand, could be deposited from hydrothermal fluids of intermediate oxidation-sulfidation state

and be associated with less advanced degrees of base-cation leaching of wall rocks (e.g.,
sericitic alteration).

Porphyry Copper and Related Deposits: 1940-1980.

The first detailed studies of advanced argillic (including acid-sulfate) and sericitic alteration
associated with relatively high sulfidation state sulfide assemblages were focussed on enargite-
bearing veins associated with felsic igneous rocks at Cerro de Pasco, Peru, and Butte, Montana
(Graton and Bowditch, 1936; Sales and Meyer, 1948; 1949). Field documentation that enargite-
bearing veins with acid-sulfate alteration commonly were superimposed on the upper portions of
porphyry copper deposits (Meyer and Hemley, 1967; Meyer et al., 1968; Taylor, 1933),
systematization of naturally occurring sulfide mineral assemblages as a function of "sulfur
content" (McKinstry, 19xx, 19xx), and experimental definition of mineral equilibria as a function
of temperature and fluid compositions (Barton et al., 1963; Hemley and Jones, 1964; Hemley et
al., 1969; ), led to increased understanding of the geologic and geochemical factors that control
the formation of very high- to high- sulfidation enargite-covellite ores versus low-sulfidation
(magnetite-bornite) to intermediate-sulfidation (chalcopyrite-pyrite) ores in porphyry-related
systems (Hemley and Jones, 1964; Meyer and Hemley, 1967; Hemley et al. 1969; Gustafson
and Hunt, 1975; Einaudi, 1977; Knight, 1977; Brimhall, 1977, 1979). At the same time, there
was increasing field evidence that some epithermal high-sulfidation deposits are somehow
linked to deeper porphyry systems (Sillitoe, 1973; Wallace, 1979). Combined with an enlarging
base of descriptive models of porphyry copper deposits (Titley and Hicks, 1966; Lowell and
Guilbert, 1970; Rose, 1970; Guilbert and Lowell, 1974; Sutherland-Brown, 1976; Titley, 1975),
data on temperature-salinity (Roedder, 1971; Moore and Nash, 1974; Eastoe, 1978) and
sources of water in hydrothermal fluids (Sheppard et al., 1969, 1971; Sheppard and Taylor,
1974; Taylor, 1974), and models of the physical and chemical nature of the magma-
hydrothermal transition and of overlying vapor-dominated systems (Burnham, 1967, 1979;
White et al., 1971; Holland, 1972; Phillips, 1973; Whitney, 1975; Henley and McNabb, 1978), an
evolutionary theme for porphyry copper and closely related deposits emerged. Although this
evolutionary model was briefly swayed from its magmatic roots (Norton, 1972; Norton and
Cathles, 1976), by 1980 the magmatists prevailed.

Porphyry Copper Systems - Characteristics

The evolutionary framework for porphyry- related deposits formed at depths of 2 to 4 km,
established by workers cited above and further refined in the early 1980's (Brimhall, 1980;
Burnham and Ohmoto, 1980; Titley and Beane, 1981; Einaudi, 1981, 1982; Eastoe, 1982;
Sillitoe, 1983a, 1983b) can be cast in terms of the observed space-time distribution of two ore-
forming environments, as illustrated in Figure 1 (A & C) and summarized in Table 2 .
Table 2. Characteristics of low and high sulphidation porphyry related copper deposits (based on Einaudi, 1982)

Low-sulfidation Disseminated High-sulfidation Lode Copper

Feature
Copper Deposits Deposits
multiple stocks and dikes associated
small, isolated plugs and dikes; post-
morphology of plutonic rocks with small batholiths; post-ore dikes
ore dikes absent
common.
post-ore porphyry dikes common absent
common and temporally associated
igneous and hydrothermal breccias not common and post-date ore
with ore
sulfides are massive in open-space
sulfides finely disseminated & in
ore textures fillings in breccia matrices, veins;
veinlets; conducive to bulk mining
less conducive to bulk mining
Mo rare; average 2 to 6% Cu, 2-4
Mo common; average 0.35 to 1.0%
oz/t Ag, Au data incomplete but high
Cu, 0.1 oz/t Ag, <0.03 oz/t Au;
metals Au present in some examples;
rarely contain significant Pb-Zn-Ag
contain major Pb-Zn-Ag in both
but, if present, only in limestone
igneous and sedimentary rocks
bornite-chalcopyrite with or without
pyrite-enargite, pyrite-covellite,
major ore-mineral assemblages in magnetite, chalcopyrite with or
pyrite-digenite, pyrite-bornite,
copper ore without magnetite, chalcopyrite-
locally hematite is abundant
pyrite; late hematite may be present
timing of pyrite introduction in
pyrite is late pyrite is early
copper ore
sphalerite is uncommon in copper sphalerite is common in copper zone,
timing of sphalerite introduction in
zone and is late relative to copper is early, and is replaced by copper
copper ore
sulfides sulfides (like Kuroko!)
zoned outward from low to high zoned outward from very high to
lateral zoning of sulfidation state
sulfidation states intermed and low sulfidation states
potassic (biotite-orthoclase- Advanced argillic (including acid
wall-rock alteration in copper zone
anhydrite) with late sericitic (quartz- sulfate) with peripheral sericitic and
of quartz-feldspathic wall rocks
sericite-pyrite) intermediate argillic
andradite-salite skarn locally
wall-rock alteration in copper zone silica-pyrite replacement bodies and
retrograded to chlorite-clay-
ofcarbonate wall rocks breccias
carbonate
"endmember" examples (note that
Twin Buttes, Christmas, Silver Bell, Magma (Superior) and Bisbee,
tops of low-sulfidation districts may
and Mission, Arizona; Santa Rita, Arizona; Cerro de Pasco, Peru;
have been eroded, and bottoms of high-
New Mexico; Yerington and Copper Yauricocha, Peru; Tintic, Utah;
sulfidation districts may be at depth
Canyon, Nevada; El Salvador, Chile Nena, Papua New Guinea
below present drilling
Examples dominated by low- Ely, Nevada; Red Mountain,
intermediate sulfidation (diss'd) but Arizona; Bingham, Utah; Cananea,
with some high-sulfidation lodes Mexico
Butte, Montana; Chuquicamata and
Examples dominated by high-
Collahuasi, Chile; Morococha, Peru;
sulfidation lodesbut with some low-
Lepanto, Philippines; Recsk,
intermediate disseminated ores
Hungary; Bor, Serbia
Low- to intermediate sulfidation environment (A): Early and/or deep stages are characterized by
potassic alteration and anhydrous skarn with disseminated/veinlet chalcopyrite-bornite-
(magnetite) related to refluxing magmatic brines (saline, and hypersaline if a vapor plume is
released) at 600-400 C, lithostatic pressure, and intermediate sulfidation-oxidation states (arrow
2, Fig. 1). This early stage is succeeded by late, superimposed and high-level sericitic alteration
of porphyry and retrograde alteration of skarn, accompanied by pyrite-chalcopyrite- (hematite),
in through-going veins. Late fluids are dominantly meteoric, boiling at 350-250 C under
hydrostatic pressures, and are characterized by moderate acididity, low-salinity, and high
sulfidation-oxidation states (arrows 5, Fig. 1). The degree of development of sericitic alteration
varies significantly at present levels of exposure in porphyry copper districts (e.g., minor at
Bingham, Utah; major at Ely (Robinson), Nevada).

High- to very high-sulfidation environment (C): Some porphyry deposits contain very late, high-
level advanced argillic alteration (encased in sericitic) with pyrite-alunite, in some cases
accompanied by digenite, covellite, and/or enargite (e.g., Butte, Montana; Chuquicamata,
Chile), in other cases barren of copper (e.g., El Salvador, Chile). Acid-sulate alteration is
localized in faults, hydrothermal breccias and around pebble dikes. Acid-sulfate fluids are of
meteoric water (arrow 7) and/or magmatic-vapor plume origin (arrow 6), at 350-200 C, near-
hydrostatic pressure, and high to very high sulfidation-oxidation states (arrow 8). In skarn or
carbonate wall-rocks, these fluids generate silica-pyrite Cu- (Au) fissures and replacement
bodies (e.g., Bisbee, Arizona; Yauricocha, Peru).

Continua and Causes

Variations on the degree of development of low sulfidation (A) versus high-sulfidation (C) fluids
in porphyry-related copper deposits, as exhibited by localities summarized in Table 2, are
controlled by local tectonic, magmatic, and hydrodynamic conditions. Formation of a "classic"
low sulfidation porphyry copper deposit (environment A, Fig. 1) would be favored by relatively
deep emplacement of multiple, non-venting, intrusions into anhydrous, unfractured rocks in a
relatively stable tectonic environment. In contrast, formation of a high-sulfidation "Cordilleran
lode" deposit (environment C, Fig. 1) consisting of massive pyritic copper ores encased in
advanced argillic and sericitic alteration would be favored by relatively shallow subvolcanic
emplacement of isolated stocks and plugs into fractured rocks saturated with meteoric water in
an active tectonic environment. Abrupt superposition of high-sulidation veins (environment C) on
to low-sulfidation disseminated ores (environment A) could result from "tectonic quenching",
such as pressure release and incursion of meteoric water due to large-scale crustal
faulting(Gustafson and Hunt, 1975; Einaudi, 1977; Brimhall, 1980; Einaudi, 1982), or by removal
of overlying rocks by erosion during rapid uplift or mass-wasting of volcanic edifices (Sillitoe and
Gappe, 1984). In some cases, tectonic quenching could effectively suppress the development of
disseminated porphyry copper deposits at (A), resulting in a lode deposit without porphyry roots
(Einaudi, 1977, 1982).

Porphyry Copper - Epithermal Gold Systems: The View from Above, 1990

With increased interest in precious metals during the 1980s, research in ore deposits shifted to
gold- rich porphyry copper deposits, epithermal systems and other environments of precious-
metal deposition. The result is important new information on: (1) geologic settings of high-
sulfidation epithermal deposits and their links to deeper magma-hydrothermal systems (Sillitoe,
1988, 1989, 1992; Heald et al., 1987; White, 1991); and (2) case studies of high-sulfidation
epithermal districts that integrate geology, geochemistry, fluid inclusions, and light stable
isotopes (Bethke, 1984; Stoffregen, 1987; Bove, 1988; Arribas et al., 1989; Deen, 1990; Bove et
al., 1990; Muntean et al., 1990; Rye et al., 1992; Vennemann et al., 1993; Hedenquist et al,
1994). These studies have lent further support to the idea that high-sulfidation epithermal
deposits have a magmatic fingerprint and that some are closely linked to deeper porphyry
systems

The present conceptual model that ties porphyries with high-sulfidation epithermal systems (in
contrast with high-sulfidation copper lodes), based on the studies cited above, is paraphrased
here from Sillitoe (1989, Fig. 9) and Rye (1993, Figs. 1 & 33). The porphyry copper environment
that occupies a position between the water- rich carapace of the magma and the overlying
transition from plastic to brittle rock, also may be of critical importance to epithermal deposits.
This volume, characterized by the presence of saline magmatic water, quasiplastic behaviour,
and low water:rock ratios, and by the absence of long-lived fractures and of meteoric water, may
be the reservoir for evolved magmatic fluids that generate epithermal ores. At the ductile-brittle
transition, saline magmatic fluids encounter open fractures and hydrostatic pressures; boiling of
these fluids results in a hypersaline brine that remains at the ductile-brittle transition (arrow 2,
Fig. 1) and a vapor plume (arrow 1, Fig.1 ) that rises to high levels where it generates barren
acid-sulfate alteration following condensation (arrow 3, Fig. 1). As the ductile-brittle transition
withdraws to deeper levels with time, metal-bearing saline and hypersaline liquid-phase fluids
that have been refluxing within the stock (arrow 2) are tapped (arrow 4) and may ascend rapidly
to high levels. These are the epithermal ore fluids (environment B, Fig. 1). If the deep
environment (A, Fig. 1) fails to evolve to environment (C), then the high-sulfidation deposit (B) is
separated from its roots (A) by a rock volume with little or no signs of hydrothermal activity.

The present challenge to students of porphyry systems is to distinguish, within individual

districts, between the model endmember processes that generate acid-sulfate fluids (vapor
plume or liquid-phase mixing?), the causes of mineralized versus barren acid-sulfate zones, and
the potential continuum between copper-rich and gold- rich high-sulfidation deposits.

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