Porphyry Lecture She Den Quist

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Porphyry systems and ore deposits: A series of annotated undergraduate

lecture slides, 2016 (Part I)
Presentation · March 2014

DOI: 10.13140/RG.2.2.32135.19363
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Porphyry systems and ore deposits February, 2016: University of Ottawa
See Sillitoe, 2010, Porphyry Systems (Economic Geology), the best overview
of porphyry deposits (also his 2005 paper in the Economic Geology 100th
Anniversary volume on supergene-altered porphyry deposits).
These notes were originally presented during two lectures to senior
undergraduates at the University of Ottawa, followed by two lectures on
epithermal deposits and their formation (also uploaded to Research Gate).
They provide an introduction to the systems and processes that form intrusion-
centered porphyry and epithermal ore deposits, a starting point to the
exploration for such deposits. Jeffrey Hedenquist, Ottawa
Lectures © Jeffrey W. Hedenquist 1

Porphyry Cu deposits account for about 70-75% of world Cu production

(Sillitoe, 2010). They form in volcanic arcs, both continental and oceanic.
The gold byproduct of porphyry Cu deposits, as well as gold in epithermal
deposits (high and intermediate sulfidation) in these intrusion-centered
systems (see Sillitoe, 2010, Porphyry Systems) accounts for about 40% of non-
placer gold production. Epithermal low-sulfidation deposits form in back arc
settings, due to crustal extension, and are not underlain by porphyry deposits.

Very schematic view of gold deposits, including arc-related porphyry and HS,
IS epithermal, plus back-arc LS deposits. Porphyry Cu deposits can be Au-
rich (shallower intrusions?) or Mo-rich (deeper intrusions?); probably not this
simple.
3
This slide shows the Porphyry system grouping (with VMS gold included with
back-arc LS epithermal, as back-arc VMS are just seawater-drowned LS
epithermal, with a bit higher salinity, speaking in terms of tectonics and
magmatism). Note that this figure does not break out back-arc settings, i.e.,
LS epithermal from HS and IS, just lumps all epithermal (see epithermal
lectures, plus slide 2 above).
Rich’s update, from Lipson’s 2014 SEG NL article, on gold; note that placers
(and paleoplacers) are not included in the pie. Since Porphyry and most
Epithermal are associated with Porphyry Systems, as is Skarn, I place
Porphyry Systems at least equal to Orogenic in gold importance.
Orogenic=1 at 80-110 Moz, 3 at 40-80 Moz, 12 at 15-40 Moz

Porphyry=2 at 80-110 Moz, 3 at 40-80 Moz, 7 at 15-40 Moz
Epithermal=2 at 40-80 Moz, 8 at 15-40 Moz
Carlin=4 at 15-40 Moz
Skarn=1 at 15-40 Moz
4
Sizes of large porphyry deposits and related magmatism and age. Inset on a-
left) lists sizes of largest Canadian (BC) deposits.
Cooke’s 2005 review, EG

Distribution, age, metal complement. Most significant regions are Central

Chile, N Chile/S Peru, and SW North America.

Basic introduction of magma sources and crustal structures that focus magma
ascent. Of course, much more complicated. See Jeremy Richard’s OGR
paper, 2011, on magmas, as well as other papers (e.g., post-collisional settings
of porphyry deposits, i.e., Iran paper in EG), and his 2007 paper in EG with
Kerrich, showing that porphyry deposits are NOT related to so-called adakites
(indeed, most “adakites” are not, but have adakitic signatures due to multiple
processes unrelated to slab melts).
7
SEG SP 16, Sillitoe volume, good discussion of the mafic input to

differentiated magmas up to MAH and above that may form porphyry
deposits.

Jeremy Richard’s 2011 schematic, basic view of the porphyry system above
the upper crustal magma at the level of neutral buoyancy and/or the
seismotectonic level, i.e., ~8-12+ km depth, from which apophyses rise to the
level of porphyry deposit formation, ~1.5 to 3 km depth.

Sillitoe’s Porphyry System, deposit types in an intrusion-centered system (he

put Carlin in the distal LS setting, but I changed to carbonate replacement).

Bingham Canyon, Utah, first open-pit mining operation, large scale mining,
started ~1902. North America’s largest gold producer (low grade but huge
tonnage); one of the 10 largest Cu deposits.

My start of explaining where P Cu deposits form, in shallow intrusive settings

in arcs, with a volcanic edifice possible. Jeff Keith and students mapped the
volcanic rocks at Bingham and postulated nearly 2 km volcanic rocks have
been eroded. Note the syn-mineral mafic dikes in the deposit, discussed by
Hattori and Keith, MD 2003, probably source of S (mafic magmas can hold
>10X S than felsic magmas, and first and foremost, porphyry deposits are
SULFUR anomalies, ~3 order of magnitude enriched from crustal, vs the ~2
order enrichment of Cu. Follow the S (comes from the mantle, i.e., largest
porphyry deposits have S ~0 permil, as noted by Hattori and Keith.

Patrick Redmond’s study of Bingham inclusions, with drillholes below the Cu

deposit, showing that deep inclusions are critical behavior (moderate salinity
once homogenized, with tetragonal xstals of chalcopyrite, i.e., Cu ~1 wt% in
this magmatic fluid, exsolved from magma). BELOW ore, this fluid separated
to vapor and hypesaline liquid on hitting its solvus, thus the 50+% NaCl equiv.
brine and <1% NaCl coexisting inclusions. Cooling of the brine led to Cu
deposition, NOT the separation (see review by Kouzmanov and Pokrovski,
2012, in Sillitoe volume). Brine is dense, remains at depth, but COUPLED (in
terms of source and timing) vapor is buoyant so can ascend (red arrow
animation) to either discharge as high T fumaroles from volcanic edifices OR
condense to form acidic condensates, source of hypogene advanced argillic
alteration.

Japanese know the source of volcanic discharges, a demon with hot breath,
stoking the magma fire.
14
Example of the vapor discharge of a deep magma (NOT the total hydrothermal
fluid, as this vapor has a salinity of ~0.1% NaCl, i.e, a brine MUST have
separated at depth, since a typical fluid exsolving from a 2-km deep magma
will be ~2 to 10 wt% NaCl. Note abundance of SO2 and HCl magmatic gases.
Photograph by Werner Giggenbach.
15
Werner Giggenbach sampling low-T marginal fumaroles in 1988.
16
More recently, vapor discharge (plus or minus some volcanic ash) has
declined, now the vapors are condensed by meteoric water in the volcanic
crater, with the condensate having a pH of 0.2. During periods over lake
overflow, the acidic condensate leaches the rock of all rock-forming elements,
including Al, Fe, etc. (soluble at pH <2), leaving only a siliceous residue (since
silica solubility is NOT a function of pH under acid conditions). Outflow to
ocean has a composition that indicates congruently dissolved rhyolite, except
for the silica. Inset, Werner Giggenbach examining the silica residue (>97%
SiO2) at Satsuma Iwojima, due to volcanic vapors condensing and the acidic
liquid leaching the rock. White Island photograph by Stuart Simmons.
17
View of Satsuma Iwojima. Note (like White Island) the outflow of acidic
vapor condensates to ocean, strong alteration of upper portion of 1000 yr old
rhyolite dome.

Satsuma Iwojima crater, atop dome, sampling fumaroles for analysis

(condensing vapor in a evacuated bottle, immersed in an ice water bath; rubber
suit and catalytic converter allows us to survive the proximity to the vapor and
its acidic condensates – acid burns around your eyes where the acids
condense).
19
View from SI summit, outflow of condensate, pH 1.1, after interaction with

rock and leaching of rock components. Magmatic vapor (star) has distinctly
different composition from seawater and meteoric water (rain, with local
meteoric at SI in blue square). Acidic springs are mixtures of vapor condensed
into local meteoric water, with 50:50, pH 1.1 to about 15:85, pH 1.7. View of
rhyolitic, leached, residual quartz (the host to potential high sulfidation
enargite and gold mineralization).
20
Acidic springs along the shore of SI. Inset shows the composition of fresh
rhyolite and acid springs, with the pattern for the rock-forming elements being
parallel, i.e., congruent dissolution of the rock by the acidic condensate, except
for silica, which is left behind as residual quartz, locally with a vuggy texture.
21
H2O-NaCl system, salinity vs P, with solvi at different T. Melt with fluid

inclusions (i.e., saturated melt); next is the critical fluid, which rises and (if at
550 C), intersects its solvus at about 700 bar and separates to liquid and vapor;
continued ascent causes liquid to increase salinity (to 55 wt% at 500 b) and
coexisting, COUPLED vapor to decrease salinity (to 0.7 wt% at 500 bar). This
accounts for the coexisting inclusions of vapor and hypersaline liquid. The
vapor may rise rapidly (erupt) from 500 b, 2 km lithostatic depth and discharge
from White Island. Slow ascent and continued loss of NaCl solubility in
vapor, the vapor may discharge passively from fumaroles, e.g., Satsuma
Iwojima, all while the dense brine remains at depth.
22
Porphyry system alteration, Sillitoe 2010. Magma (black arrow) and critical
fluid (grey). I have animated the porphyry evolution, first early stage, high
temperature, COUPLED potassic (deep brine. forming biotite, kspar, mt) and
advanced argillic (condensed vapor). Cu sulfides may deposit from brine
(dark blue) in qtz stockwork (veins are typically wavy, as they were deformed
after formation because under high T the rock is ductile, and hence at
lithostatic P). The vapor (orange) does NOT transport significant metals, and
thus the formation of the lithocap is essentially BARREN in this stage.
Residual qtz is formed at lowest pH in proximal position, out to alunite,
kaolinite, etc. (more in epithermal lecture).

Porphyry system, intermediate stage (deep fluid is STILL 100%

MAGMATIC), forming phyllic alteration (Note that there is commonly a
misconception from 1970s that phyllic is due to meteoric water, but this is not
correct; see Hedenquist et al., 1998, EG). This stage has a moderate salinity
(5-10%) fluid, ie., UNSEPARATED critical behavior magmatic fluid, which is
cooler in this intermediate stage and does not intersect its solvus. The fluid is
white-mica stable, and any veins that form are straight and open (hydrostatic
P) since the rock is brittle at the lower T, <350 C. This fluid has a density that
allows it to rise into the lithocap, and if so, it cools from chalcopyrite to
enargite (intermediate to high sulfidation state stubility; see Einaudi et al.,
2003, SP 12), thus mineralizing residual qtz in enargite and gold. Or this fluid
may ascend to margin of system and form IS epithermal veins with white mica
halos (white mica does not form in the residual qtz since there is no K in the
rock). Post-phyllic alteration, dominated by clays (argillic), is formed after
magmatic fluids no longer enter the system (magma has crystallized at depth),
due to meteoric-water convection around the still-hot intrusion.

Usually not enough time for this. See Shinohara and Hedenquist, 1997, J Pet.
Reason for shift from high T upflow (with fluid separating to brine and vapor,
creating potassic and adv arg alteration) to lower T magmatic upflow relates to
the convection of the magma chamber. At <50% xstals, crstallization during
magma convection occurs rapidly and exsolution occurs rapidly. At >50%
xstals, the magma becomes stagnant, cools by conduction, and the exsolution
slows an order of magnitude (next slide), so lower T fluid does not intersect its
solvus, does not separate; forms white mica. Thus two fluids originate from
same magma chamber, but 2 different cooling paths (3rd slide below).
25
There is an order of magnitude decrease in the rate of crystallization, and

hence rate of crstallization-driven exsolution of fluid after ~50% crystals; the
100 km3 magma body crystallizes in ~30 k yr. See Mercer et al., 2015,
Economic Geology, for age of porphyry systems, as well as recent work by
Weis, 2014. Inset photograph by Werner Giggenbach.
26
Slower exsolution of fluid from a stagnant (non-convecting) magma means

slowing advection, and thus the T at the level of the top of the apophyses is
lower, shifting from high T potassic to low T phyllic alteration, and lithostatic
to hydrostatic P due to the rock becoming brittle below ~400 C.
27
The same magma, crystallizing and convecting, then becoming stagnant at

~50% crystals, is accompanied by two paths of ascent of the essentially same,
early and late exsolving fluid. The early fluid advects rapidly, and this causes
the hot fluid to intersect its solvus and separate to brine and vapor (the latter
discharging from volcanic edifices), whereas the later fluid, advecting more
slowly, never separates (although it will start to boil at shallow depth).
28
Fault reconstructed San Manuel porphyry in SW US, with alteration zoning

made famous by Lowell and Guilbert, 1970. Note that phyllic is shown as a
halo to the central potassic zone. Rather, phyllic is a later overprint of potassic
(which zones out to propylitic, not phyllic). In 2nd figure, below,, the sulfides
are zoned, with the ore suggested to be a “shell”; rather, in many cases, the
low-grade core of a deposit is due to a late syn-mineral intrusion being lower
grade. Still, these observations helped to start the construction of realistic
zonation models of porphyry deposits. Lower right, Seedorff et al., 2005,
simplification of Lowell and Guilbert, showing early feldspar-stable alteration
on the intrusion (potassic), overprinted by hydrolytic alteration (phyllic);
external fluids cause the propylitic alteration. Note that these figures dash the
(eroded in Arizona) upper portion of the deposit, possible propylitic? In fact
we now know that acidic vapor condensates form lithocaps of advanced
argillic alteration over and offset from the intrusions (see above).

Seedorff et al., 2005, combined the alteration due to hydrolytic attack, both the
early and shallow advanced argillic alteration (of the lithocap) and the later
phyllic stage of overprint on potassic alteration. These two are distinctly
different fluids, early vapor condensate (vapor coupled to the deep brine) vs
the later evolution of the magmatic liquid, respectively (see Hedenquist et al.,
1998, Economic Geology, for details).

Porphyry – iron oxide (Cu) systems at Yerington. Intrusion apices show by

potassic (biotite) alteration below Cu, with more shallow QSP (phyllic, quartz-
sericite-pyrite), grading up to advanced argillic, pyrophyllite and/or alunite.
Heating pathways of fluid, here basinal brines convecting toward intrusions,
causes Ca alteration (see next slide), and more shallow Na alteration, whereas
cooling causes K metasomatism. In places the Ca alteration may be related to
shallow Fe metasomatism and (Cu) skarn.

Heating of a fluid cases Na-Ca alteration (including propylitic), whereas the

same fluid cooling results in potassic (biotite, Kspar) at high T, or phyllic
(white mica) at low T.

Simplification of the Yerington district. Na-Ca alteration forms on the heating

pathway of an external (basinal) liquid, distinct from the magmatic fluid
exsolved from intrusions which forms K-dominated alteration on cooling
(slide 32). Section courtesy of Dr. John Dilles, Oregon State University.

Seedorff time-depth diagram (upper left), showing intrusions to 3 km depth,

early potassic alteration, then as the system cools, transition to sericitic (still
magmatic), then late argillic and carbonate, caused by meteoric water
overprint. Critically, Seedorff left off advanced argillic lithocap, which is a
critical part of the system; so did Lowell and Guilbert. Why? They all live in
Arizona, where there is 1+ km of erosion, such that the lithocap is not
preserved. So I have added it here, in red, as potassic (from brine) is coupled
to adv arg (from vapor); see upper left diagram in slide 31, which Seedorff also
got wrong by somehow linking adv arg with sericitic, even though the former
is formed early in the system, due to phase separation that does not occur
during phyllic alteration.

During the phyllic stage, white mica (muscovite) commonly grades up to

pyrophyllite (which has only been recognized for the last 15 years or so, since
it is easily identified by SWIR, e.g., PIMA or Terraspec; most porphyry
deposits have caps of this mineral, at the transition to the adv arg lithocap.
Pyrophyllite overprints muscovite at El Salvador, Chile. Why? Because a
muscovite-stable fluid (with andalusite) was cooling A to finally intersect
pyrophyllite stability B; further cooling can drive this fluid into dickite
stability C. This is not a descending fluid, but rather the isotherms are
retracting such that what was 375 C and muscovite stable becomes 325 C and
pyrophyllite stable. Note that an adv arg fluid with low K/H (low pH, high
H+), stable with alunite and pyrite at the margin of a lithocap, can be in
equilibrium with pyrophyllite in a different environment, different fluid
compositions (the musc-pyroph liquid has a similar O-H composition, whereas
the alun-pyroph fluid has a signature indicating that it formed from vapor
condensation; see Watanabe and Hedenquist, 2001, EG).

Seedorff et al., 2005. K/H vs Mg/H diagram, T slices, showing that the same
composition fluid will evolve in mineral stability on cooling, particularly after
phase separation (red and yellow, brine and vapor). Adding B to the system
increases the stability of tourmaline or dumortierite over that of musc as well
as andalusite or Kspar.

Every porphyry is different, particularly related to the nature of the host rocks
and the intrusion, but the similarity is that alteration mineral assemblages are
spatially zoned, and there is lower T assemblages that overprint higher T
assemblages.

Veins: early (potassic stage, high T ductile rock) veins have no centerline or
obvious alteration halo (lithostatic P), whereas the intermediate (phyllic stage,
lower T, brittle rock) veins have centerlines, open spaces, and typically have
white mica halos. The later veins (sometimes called D veins clearly cut the
early A veins.

Vein stages: Cu grade typically follows density of early to intermediate stage

veins. Host rock is cut by all veins, as is the earliest intrusion. Early
intermineral intrusion may cut some early A veins, with vein clasts hosted in
the intermineral intrusion, but this may also be cut by high T A veins. Late
intermineral intrusions (low grade) cut all A veins, but some transitional B and
intermediate D veins may be present. Late to post mineral intrusions cut all
veins, no grade. FSE deposit, early finer veins, with mt, cut by several stages
of veins. Sulfides can reopen earlier quartz veins, ie., sulfide in quartz vein
may have reopened the centerline, since a similar sulfide-only vein cuts across
quartz veins. Need to be observant.

Los Pelambres porphyry, Chile (SP 16), showing open-pit mine centered on
the area of higher vein density (i.e., higher grades). Earliest veins may be
biotite and/or magnetite veins, then cut by early A veins of quartz, which may
also contain mt. B transitional veins are commonly Mo rich. Intermediate D
veins have pyrite ±base metal sulfides, with white mica halos.

Halilaga porphyry discovery, stockwork veins, adjacent to a barren lithocap,

Turkey. Early exploration assessing lithocaps, and by mistake the soil
geochem line was run into the valley (if geologists had walked the valley they
would have seen the outcropping porphyry stockwork veins). Core shows
(below oxidized zone), early intrusion rich in veins, and Cu and Au, then an
early intermineral intrusion with 0.6 Cu, Au, followed by a later intermineral
intrusion with fewer veins and low grade, 0.2 Cu, Au. The bulk grade of the
deposit is 0.3 % Cu, 0.3 g/t Au, due to the abundance of the later intrusions
diluting the early high grade veins. Drill core photographs from Pilot Gold
website.

This is a good example (Bajo de la Alumbrera, Argentina) showing the sharp

variation in vein density due to different intermineral intrusions, with Cu
grades (next slide) related to vein density (in animation). NB: don’t drill
vertical holes into untilted porphyry deposits, as they commonly have steep
intrusions and veins, and one may either drill down a single narrow but high
grade early intrusion, or alternatively down a low grade late intrusion.

This is a good example (Bajo de la Alumbrera, Argentina) showing the sharp

variation in vein density due to different intermineral intrusions, with Cu
grades related to vein density (in animation). NB: don’t drill vertical holes
into untilted porphyry deposits, as they commonly have steep intrusions and
veins, and one may either drill down a single narrow but high grade early
intrusion, or alternatively down a low grade late intrusion.

Bingham, the density of veins (at least early to transitional) can be zoned
around causative intrusion (note that this is one of the world’s largest porphyry
deposits). Either density of vein frequency (easier to log) can be used. Early
qtz-stockwork (A) veins, transitional qtz-Mo (B) veins, and intermediate QSP
(D) veins, the latter having a peak density away from this porphyry. See
Gruen’s plan maps for more details, if interested (EG).

Buried porphyry Cu deposit in AZ, 0.5 and 0.2% grade shells projected to the
surface; zoned sulfides, py to py-cp to cp-py to cp-bn with increasing depth
toward the core.

Mapping the vein density (by John Proffett and colleagues) at surface shows
that the EH (early halo) veins show a distinct zonation pattern; if only this
pattern was drilled, >5-10% EH vein density, the 0.2 to 0.5% Cu shell would
have been intersected at ~400 m depth. D veins show a similar pattern,
although there is a D vein concentration on the margin of the system as well.

Details of paragenesis and intrusions, veins, alteration.

48
View east over El Salvador, Chile, shortly after discovery in late 1950s. QM
pit is on alter area north of peak, but main deposit (block cave) is below the
peak and pyrophyllite “cap” with muscovite (phyllic) at lower elevation; all
surface exposures are supergene oxidized. Gustafson and Hunt, 1975.

Mid 1950s Anaconda started to explore in the Old Camp area, favored by
management (few roads into the area). Geos favored Indio Muerto, and finally
got a small bulldozer to pull a rig up the hill (last lslde). First one or two holes
were disappointing, management wanted to get the focus back to Old Camp,
but geos sort of ignored orders and about 4th -5th hole cut good grade. The
zoning of this deposit underground is well known (Gustafson and Hunt, 1975,
a classic paper), but due to the rapidity of discovery, the surface alteration was
not mapped in detail. Cu introduction was related to the 44-42 Ma intrusions
into the Paleocene rhyolites and diorites (flows and domes).

Surface geology, with the L (Late) granodiorite porphyry intruded in the

middle of early intrusions. Indio Muerto up to ~3300 m elevation (thick blue
line is the present glory hole over the block cave). Cu ore at 2600 m elevation
shown, which looks like a halo to the L porphyry (yellow), but in fact the L
porphyry is mostly post Cu, and the L porphyry took a bite out of the Cu ore
body (note that the surface distribution shown of L porphyry is not the same as
its distribution on the 2600 m level).

Watanabe and Hedenquist, 2001, EG, determined the alteration zoning at the
surface, >4 km2 of muscovite alteration to marginal propylitic. The inner zone
of muscovite coexists with andalusite, and the purple shows >30% andalusite
(can recognize with a hand lens).

This slide shows the higher elevation (above 3100-3200 m) zone of

pyrophyllite overprint of muscovite, and the 2600 m Cu ore zone.

Andalusite and muscovite of the phyllic stage, with later pyrophyllite overprint
of muscovite (dark grey replacing light grey muscovite along cleavage planes,
lower right image), due to cooling (classic Hemley diagram).

View SE, QM pit to left, Indio Muerto with its “cap” of pyrophyllite, and the
older rhyolite dome replaced by late quartz-alunite shown. Note road from
town to mine was located over the pediment, and geos drove this for 4 decades
until, in the early 1990s, a well-known British consultant noted evidence for
exotic Cu near the open pit and proposed testing the pediment for exotic Cu. A
blast hole rig was used and identified a significant exotic Cu resource 10-20 m
deep. Think laterally. Photograph by Yasushi Watanabe.

The latest event was a series of radial “pebble dikes”, hydrothermal breccias,
with an assemblage of advanced argillic minerals; the muscovite comes from
fragmented wall rock. One zone to the SW shows quartz-alunite replacement
of an early rhyolite lava dome to the SW, which can be seen on the previous
view.

O-H diagram, composition of volcanic vapor and location of meteoric water

line shown. Local meteoric water approximated by the composition of the
supergene kaolinite. Deep hydrothermal biotite is similar to the composition
of water in felsic magmas. The overprint of muscovite at shallow levels and at
the surface indicates that the phyllic alteration was dominated by magmatic
water. Pyrophyllite and dickite replacing muscovite, due to cooling, has a
similar isotopic composition. By contrast, pyrophyllite with alunite in the late
hydrothermal breccias is distinctly different, sitting on a vapor-meteoric water
mixing line expected for acidic condensates causing the late advanced argillic
alteration (due to degassing of a late, deeper intrusion to the SW of the main
porphyry deposit).

If mapping over the original surface, this would be the alteration map, with
muscovite overprinting early potassic, then later pyrophyllite overprinting
proximal muscovite and andalusite, followed by later radial hydrothermal
breccias with advanced argillic alteration.

Animation shows early potassic alteration, encapsulated with sulfides in early

veins; there may have been a lithocap that has been eroded, with paleosurface
~1 km above the top of Indio Muerto. Then the phyllic overprint of
muscovite, followed by collapsing isotherms and retrograde pyrophyllite, then
late hydrothermal breccias with advanced argillic alteration (related to a late
deep intrusion?).

Sillitoe’s schematic section, eroded ~1 km to show the alteration below the

lithocap that would be exposed.

Sulfide zoning at 2600 m ore level, and distribution of host andesite, then the
X, K and finally late L porphyry intrusions. Compilation by Marco Einaudi,
unpublished.

Schematic cross section showing in greys the early potassic stage zoning of
sulfides, followed by the phyllic (sericitic) intermediate stage overprint of
deep tennantite in D veins, grading up to enargite in the D veins due to
cooling, and high sulfidation state assemblages along the erosion surface
(oxidized except where preserved encapsulated in quartz veins). Compilation
by Marco Einaudi, unpublished.

Definition of sulfidation states, T vs fugacity of S, from porphyry to

epithermal T ranges. Tennantite (tn), IS, transition to enargite (en), HS, is
similar in position to that of cp//py+bn (not just bornite, bn, but must be
coexisting with py to be HS).

Arc magmas are close to rock (Fe2+/3+) buffer at magma T, then fluid cools,
starting in LS, to IS and – IF fluid reacts with rock buffer, it stays in IS field;
but where rock buffer is leached, in the residual quartz lithocap, a fluid that
enters the lithocap will keep cooling and moving left, into HS enargite stability
(same in large qtz veins, or in quartzite, no buffer so cooling causes an
increase in sulfidation state). See Einaudi et al., 2003.

The sulfide zonation caused by cooling around an intrusion leads to regular or

typical patterns of sulfides, predictable (typically increasing in sulfidation state
with cooling, slide 64, and with time), e.g., El Salvador or Bingham. Observe
and record coexisting sulfide mineralogy (where not oxidized), either in
outcrop (over Bingham) or in core. Sections compiled and prepared by Marco
Einaudi, unpublished.

In the next two slides, we summarize sulfide assemblages in some porphyry-

Cu deposits, arranged from left to right in a sequence from early high
temperature to later low temperature assemblages. The assemblages listed on
the right are late on the scale of the orebodies. The assemblages are color-
coded for sulfidation state as in previous slides. The main ore assemblages are
indicated by the red box outline.
This slide shows deposits where most of the ore consists of bornite-
chalcopyrite-magnetite. Cp-py is typical of late stages with sericitic alteration,
but commonly not ore-grade, and a few of the deposits listed evolved to high
and/or very high sulfidation states with advanced argillic alteration. This is
one type of porphyry deposit, most Cu introduced early, with potassic, stable
with mt (and with a mag high).

In this second slide, we see a shift toward ore consisting of both bornite-cp and
chalcopyrite-py, with magnetite absent or minor (top 6 deposits) to ore
consisting mostly of cp-py (bottom 3 deposits). Of the deposits listed, Butte
and Chuqui contain a dominant portion of the ore in large vein systems that
contain sulfide assemblages indicative of very high and high sulfidation states.
Type 2 porphyry deposits has much of the Cu associated with later phyllic
stage, even shallow adv arg alteration, with pyrite, higher sulfidation states,
and no mt (i.e., no mag high related).
The key points of these two slides are that (1) most porphyry copper deposits
contain an ore assemblage that defines intermediate sulfidation states; and (2)
at the scale of deposits, pyrite is late relative to cp and bornite.

Summary of two endmember styles. See Einaudi et al., 2003.

Log fS2 – 1000/T diagram, contoured for RS, illustrating fluid environments in porphyry
copper, porphyry-copper related base-metal veins, and epithermal Au-Ag deposits in terms of
a series of possible cooling paths that are influenced by processes discussed by Einaudi et al.
(2003). Fluid environments are based on sulfide assemblages and temperatures summarized by
Einaudi et al., and sulfidation reactions from Barton and Skinner (1979). Arrow labeled
"porphyry Cu-Au-Mo" refers to early- and intermediate-age assemblages deposited at
approximately 500 to 350°C and low to intermediate sulfidation states. Arrows labeled "N"
and "O" represent deviations from the main-line environment. Transition to late assemblages
at high sulfidation states and to porphyry-related "zoned base-metal veins" at or below 350°C
is indicated by gray arrow labeled "T". Sulfide assemblages in the latter deposits describe a
return from very high sulfidation to the intermediate sulfidation states of the "rock buffer".
Similarly, HS epithermal deposits consist of an early Cu-rich, high sulfidation state
assemblage followed by a Au-rich stage at intermediate sulfidation states. IS epithermal
deposits (not shown) form at about 250 °C and mostly at intermediate sulfidation states. LS
epithermal gold veins are shown near 200 °C and at low to intermediate sulfidation states near
the rock buffer. Other porphyry-type deposits that form at low and even very low sulfidation
states (dark, thin arrows labeled "Mount Pleasant" W-Mo and related Sn-Zn-Cu veins, and
parts of Henderson Mo (labeled "H"; see Einaudi et al., 2003) are shown for contrast to
porphyry Cu and related vein deposits.

Most porphyry deposits likely form over about 10e5 years (unless many
sequential deep intrusions); if longer, the paleosurface may be degraded and
lead to a collapse of shallow alteration on deeper formed alteration. Inset,
with time and more shallow depth, both reactivity and sulfidation state
increase, as indicated by mineral assemblages.

Final example, the Far Southeast porphyry Cu-Au deposit in the Philippines
that is associated with the Lepanto lithocap-hosted high sulfidation deposit. A
qtz-alunite lithocap formed along the basement unconformity with overlying
pyroclastic rocks, exposed by river erosion. Dashed line shows location of
cross section in the next slide.
71
Cross section through the Lepanto enargite-Au HS ore body, with 70% of ore
hosted in the Lepanto fault, rest in the lithocap of residual quartz (grey) that
formed (mushroomed) along the unconformity between basement and dacitic
pyroclastic rocks. Where unconformity is exposed by river erosion, the distal
quartz-alunite forms cliffs (photo). If lithocap were drilled, there would be no
roots to silicic residual quartz and enargite. Rather, projecting unconformity to
major structures (e.g., fault offset of post-mineral Bato dacite) would provide a
potential target to test, i.e., the feeder zone (see epithermal lecture on HS).

Extent of basement rocks, particularly exposed in river valley. Approximate location

of previous cross section, cutting Lepanto fault, shown. Series of NW-trending faults
are splays of the major Philippine fault.

~2 Ma Imbanguila dacite porphyry (domes) and pyroclastic rocks, sourced from

below domes (see long section below).

Bato dacite porphyry and pyroclastic rocks, <1.5 Ma (likely related to syn-mineral
intrusions).

Alteration in outcrop. Quartz-alunite lithocap outcrops along unconformity over
basement over distance of ~7 km, SE-NW, with some also at higher elevations to east
(~1400 m), along with dickite and kaolinite. Two areas of stockwork veins has white
mica and pyrite, and one area shows illite with smectite. Quartz-alunite forms cliffs
along unconformity (photo right; see slide 71), and lithocap has dickite-kaolinite
above and below (photo left).
76
Quartz-alunite returned gold values of 12 to 49 ppb, anomalous but not high. Silicic
structures with quartz-alunite halos (like the Spanish workings from 1800s, photo)
return 1-4 g/t Au. There are two breccias, to west a phreatomagmatic deposit with
clasts of porphyry altered and mineralized intrusions, and to east, a hydrothermal
breccia with Cu oxide cement. Where to drill test?
77
These are known deposits, with Lepanto silicic-hosted enargite, FSE porphyry and
Victoria-Teresa veins mostly blind, projected to surface. NW extent of Lepanto
outcropped near the Spanish workings, and south extent of Teresa veins outcrops in
stream valley at Nayak. FSE porphyry below the breccia with Cu oxide cement. See
related alteration in outcrop, previous slide. Next slide is long section (yellow line) in
plane of Lepanto fault. Mohong Hill and Buaki porphyry prospects outcrop (see slide
71 for Mohong Hill) but are small and low grade.
78
78
Long section in plane of Lepanto fault, showing the basement (Balili) and vent
source of Imbanguila (~2 Ma), with Lepanto ore in fault (from ~700 to 1100 m
elevation, rising with unconformity to NW). The porphyry halo of ore is
shown, with the modeled shell extending from ~500 masl to 400 m below sea
level (animation), with Cu (0.7%), Au (1 g/t) and Mo (100 ppm) grade shells
not coincident exactly. Porphyry veins with sulfides are largely related to
chlorite-white mica overprint. Inset vein photograph from Gaibor et al., 2013,
plus the grade shells.

Potassic stage, deep vapor ascends and is condensed by meteoric water (see O-
H trends; Hedenquist et al., 1998), and acidic condensate leaches the rock
along the unconformity in the plane of the Lepanto fault (the long section
plane). Barren residual quartz and a halo of qtz-alunite is created.
Photograph by Zhaoshan Chang. Next slide…

If a subsequent phyllic overprint of lower salinity liquid ascends and flows

through the lithocap, bringing Cu and Au; cooling in the residual qtz causes
deep chalcopyrite to shift to HS enargite stability (cementing brecciated
residual quartz, inset).

Stable isotope data on biotite (potassic), similar to water in felsic magmas (B.
Taylor, 1992), whereas same-age (`1.4 Ma, i.e., coupled) alunite (advanced
argillic lithocap) is about 10-20 permil H heavier (fractionation between
hypersaline liquid and vapor, cf. Horita). Vapor mixes with groundwater
(likely steam-heated to ~100 C) and is further diluted during flow to the NW.
Illite in the core of the porphyry has a similar magmatic signature during the
phyllic alteration overprint (<1.35 Ma), with illite on the margin, as well as
pyrophyllite (green) being diluted with meteoric water. As this illite-stable
fluid rises to the lithocap (~350 C, 5 wt% NaCl, inset), it is diluted by meteoric
water, and the enargite-hosted fluid inclusions record this dilution and cooling
during flow to the NW; diluent is ~100 C at nil salinity, i.e., steam-heated.

What if this deposit (formed at 1.4-1.3 Ma, dates of potassic biotite and
lithocap alunite, 1.4 Ma, and overprinting white mica, 1.3 Ma) were eroded?
Most resistant would be the silicic lithocap. If this were drilled, deep holes
would miss the porphyry. Rather, drilling in the “valley” of quartz-alunite,
maybe some pyrophyllite and muscovite (and stockwork veins? Cf. Halilaga,
Turkey, and below, Perol in Peru) would penetrate the porphyry, offset from
the location of the lithocap, which sits on the shoulder of the porphyry
(Hedenquist and Taran, 2013, EG).
83
How to explore such a large quartz-alunite lithocap, since the mineralogy does
not point to the porphyry? Over 4 km long lithocap, hosting the Lepanto HS
deposit proximal to the underlying Far Southeast (FSE) porphyry deposit, with
the Victoria IS veins just 500 m or so distant from the porphyry. Photograph
by Zhaoshan Chang.

Alunite related to lithocap has a low SWIR (short wave infrared) feature to the
NW, and a higher absorption feature to the SE; this can be measured in the
field camp. Higher feature in nm is closer to the known porphyry. Why?
Wavelength position of this feature shifts to higher values with more Na in
alunite (natroalunite), and experimental data (Stoffregen) has shown that Na-
rich alunite forms at a higher T than K-rich alunite. Thus the high wavelength
SWIR feature indicates Na-rich alunite that formed at a higher T, closer to the
porphyry heat source; K-rich formed in a distal, cooler position. Both alunite
crystals look the same, but SWIR allows the distinction to be made in the field
camp. This is one tool to help in mapping, one observation to add to all others
when seeking information on the proximal part of the lithocap, near the feeder
zone (which has the highest grades, if mineralized), which will also be
proximal to the underlying intrusive heat source and potential porphyry Cu
deposit.

Geophysical surveys can also contribute to exploration for porphyry deposits

(e.g., chargeability highes due to sufldes, below resistivity highes due to
residual quartz lithocaps). Porphyry deposits are thought to be associated with
magnetic highes, but recall the Type 1 vs type 2 deposits. FSE is a case where
the early magnetite has been destroyed by the phyllic overprint, resulting in a
magnetic low.
FSE sits on the SE end of the Lepanto deposit and the host lithocap. FSE has
mt with deep potassic alteration, but about 900 m below the surface. Above
this level, the phyllic overprint has destroyed the mt signature, and therefore
the porphyry shows up as a mag LOW (RTP), not as a high.

Mineral Park, AZ, was one of the porphyry systems recognized early on with
marginal base metal zoned out to precious metal veins in the district. This has
been modeled (evolution of fluid composition and processes; Kouzmanov and
Pokrovski, 2012, SEG SP 16) to show that such zonation, from Cu-Mo to Zn-
Pb, Ag-Pb and Au-As-Sb, is predicted. Next lecture, move up, and out, to the
epithermal environment (blue outline).

Morococha, Peru, with carbonate replacement mantos and skarns plus IS veins
in a district, centered on an intrusion that is related to the 2 Bt Toromocha
porphyry Cu system. Clear zonation in the polymetallic system around the
porphyry center, all part of the porphyry system.

Recall the distribution of lithocap and porphyry at Lepanto-FSE, particularly if

the system were partially eroded, with lithocap sitting on the shoulder of the
deeper porphyry. In this case, 10 km east of Yanacocha, Peru, a lithocap was
assessed (lithocaps at Yanacocha are gold mineralized), but this one, Cocañez
was found to be barren (<100 ppb Au), so the geologists left. Subsequently,
another group traveling up the valley on mules, following a gold in stream-
sediment anomaly, stumbled on outcrops in the valley of sheeted veins that
were the top of the Perol porphyry Au-Cu deposit, of the same age as the
barren lithocap (note the sheeted porphyry veins that crop out – discovery site,
lower right – are parallel the the N-S silicic ribs in the lithocap ~1 km north).
Geologists must walk the area, and not be focused only on one style of target.

If a system is eroded (e.g., Sillitoe’s porphyry system, locally to ~1 km depth),

part of a lithocap, the most resistant, may be preserved. Even if mineralized, it
may be small due to erosion, or it may be barren. Do not walk away. What is
the potential for intermediate sulfidation (IS) veins (see next lecture) being
present on the margin of the intrusion-centered system? What is the potential
for stockwork veins to be present in the adjacent valley (cf. Halilaga below
Kunk, or Perol below Cocañez, and other examples?; also in the epithermal
lecture, the barren Chucapaca, Peru, lithocap and associated intermediate-
sulfidation diatreme-related Canahuiri deposit). Look for such porphyry veins,
as well as white mica and/or pyrophyllite alteration. Do not necessarily drill
below the lithocap (cf. Lepanto example), but consider if the porphyry target
may be offset.
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Porphyry systems and ore deposits: A series of annotated undergraduate

Presentation · March 2014

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Lectures © Jeffrey W. Hedenquist 1

Porphyry Cu deposits account for about 70-75% of world Cu production

Lectures © Jeffrey W. Hedenquist 2

Orogenic=1 at 80-110 Moz, 3 at 40-80 Moz, 12 at 15-40 Moz

Cooke’s 2005 review, EG

Lectures © Jeffrey W. Hedenquist 5

Distribution, age, metal complement. Most significant regions are Central

Lectures © Jeffrey W. Hedenquist 6

SEG SP 16, Sillitoe volume, good discussion of the mafic input to

Lectures © Jeffrey W. Hedenquist 8

Lectures © Jeffrey W. Hedenquist 9

Sillitoe’s Porphyry System, deposit types in an intrusion-centered system (he

Lectures © Jeffrey W. Hedenquist 10

Lectures © Jeffrey W. Hedenquist 11

My start of explaining where P Cu deposits form, in shallow intrusive settings

Lectures © Jeffrey W. Hedenquist 12

Patrick Redmond’s study of Bingham inclusions, with drillholes below the Cu

Lectures © Jeffrey W. Hedenquist 13

Werner Giggenbach sampling low-T marginal fumaroles in 1988.

Lectures © Jeffrey W. Hedenquist 18

Satsuma Iwojima crater, atop dome, sampling fumaroles for analysis

View from SI summit, outflow of condensate, pH 1.1, after interaction with

H2O-NaCl system, salinity vs P, with solvi at different T. Melt with fluid

Lectures © Jeffrey W. Hedenquist 23

Porphyry system, intermediate stage (deep fluid is STILL 100%

Lectures © Jeffrey W. Hedenquist 24

There is an order of magnitude decrease in the rate of crystallization, and

Slower exsolution of fluid from a stagnant (non-convecting) magma means

The same magma, crystallizing and convecting, then becoming stagnant at

Fault reconstructed San Manuel porphyry in SW US, with alteration zoning

Lectures © Jeffrey W. Hedenquist 29

Lectures © Jeffrey W. Hedenquist 30

Porphyry – iron oxide (Cu) systems at Yerington. Intrusion apices show by

Lectures © Jeffrey W. Hedenquist 31

Heating of a fluid cases Na-Ca alteration (including propylitic), whereas the

Lectures © Jeffrey W. Hedenquist 32

Simplification of the Yerington district. Na-Ca alteration forms on the heating

Lectures © Jeffrey W. Hedenquist 33

Seedorff time-depth diagram (upper left), showing intrusions to 3 km depth,

Lectures © Jeffrey W. Hedenquist 34

During the phyllic stage, white mica (muscovite) commonly grades up to

Lectures © Jeffrey W. Hedenquist 35

Lectures © Jeffrey W. Hedenquist 36

Lectures © Jeffrey W. Hedenquist 37

Lectures © Jeffrey W. Hedenquist 38

Vein stages: Cu grade typically follows density of early to intermediate stage

Lectures © Jeffrey W. Hedenquist 39

Lectures © Jeffrey W. Hedenquist 40

Halilaga porphyry discovery, stockwork veins, adjacent to a barren lithocap,

Lectures © Jeffrey W. Hedenquist 41

This is a good example (Bajo de la Alumbrera, Argentina) showing the sharp

Lectures © Jeffrey W. Hedenquist 42

This is a good example (Bajo de la Alumbrera, Argentina) showing the sharp

Lectures © Jeffrey W. Hedenquist 43

Lectures © Jeffrey W. Hedenquist 44

Lectures © Jeffrey W. Hedenquist 45

Lectures © Jeffrey W. Hedenquist 46

Details of paragenesis and intrusions, veins, alteration.