Porphyry and Epithermal 101

Hydrothermal alteration in silicate rocks

Forma&on(of(a(porphyry(Cu(deposit(((
interplay*between*magma/c*and*hydrothermal*processes*

Examples from Reko Diq

porphyry Cu-Au, H15 complex,
Pakistan

Richard M. Tosdal, Ph.D., PGeo

PicachoEx LLC (U.S.A)
rtosdal@gmail.com

SEG student chapter, UNI,

Lima, Peru, October 2015

Summary of Igneous Processes

Magma compositions are variable, & dictate ore metal suite
Trace element contents are also unique to each magma
As magma crystallizes, it saturates in water-rich fluid rich
in chlorine & sulfur, and this forms hydrothermal ore fluid.
During crystallization a common suite of incompatible
elements is concentrated in last melts, & can then be
incorporated into the HT ore fluid.
So, in the porphyry copper hydrothermal footprint, a
similar suite of ore metals and trace metals are
transported --- can be potentially used for vectoring

Modied*from*Dilles,*1987*

Magma%c'Fluids:'
Exsolved'uid'is'primarily'H2O;'
Cl>'(chloride)'is'dominant'anion'in'most'exsolved'hydrothermal'
uid,'composing'up'to'20'molal,'commonly'3>6%,'but'1'to'50'
wt.%'NaCl;''
F>'may'be'equally'important'in'Sn,'Mo'granites,'pegma%tes;'''
HS>,'HSO41>,'CO32>'are'subordinate.'''
Fluids*released*from*typical*metaluminous*granites*are*charge*
balanced:***
total'Cl>'+'HS>'+'HSO4>''
'''''''''''''''='H+'Na+'+'K+'+'2.3(Fe+2'+'Fe+3)'+'2Ca+2'+'2Mg+2'+'2Mn+2.''
Magma%c'Cl>rich'solu%ons'are'slightly'acidic'(HCl).'''

Typical Pathfinder Elements in Magmas

Metals in magma
& fluids

Metal

Continental Crustal
Behavior in
Hydrothermal Complexation
Background (ppm)# Silicate Melt
Chloride
Sulfide
__________________________________________________________________________
Chalcophile Metals
Ag (silver)
0.08
Incompatible
XX
X
As (arsenic)
1
Incompatible
X
X
Au (gold)
0.002
Incompatible
XX
XX
Bi (bismuth)
0.06
Incompatible
X
X
Hg (mercury)
0.08
Incompatible
X
XX
Co (cobalt)
10
Compat in Olivine
XX
-Cr (chromium)
140
Compat in FeMag
XX
-Cu (copper)
75
Incompatible
XXX
X?
Mn (manganese)
1400
Compat. in FeMags
XXX
-Mo (molybdenum) 1
Incompatible
--Ni (nickel)
20
Compat in Olivine
XX
-Pb (lead)
8
Compat. in Feldspar
XXX
-Sb (antimony)
0.2
Incompatible
X
X?
Se (selenium)
0.05
Incompatible
X
X?
Te (tellurium)
0.001
Incompatible
X
-V (vanadium)
190
Compat. In FeMag & Ox
XX
-Zn (zinc)
80
Compat. in FeMags
XXX
--

Crea&on(and(destruc&on(of(permeability(
Hydrothermal'altera%on'
creates'permeability'
through'hydrofracturing'
and'destroys'permeability'
through'mineral'
precipita%on.'
'
Repe%%ve'process'with'
repeated'uid'pulses'
'
External'uid'interacts'
with'magma%c>
hydrothermal'uid'at'
interface..''Interac%on'via'
altera%on'mineralogy'

Compatible can stay in magma

Incompatible can go into fluid
Many trace elements chloride
complexed, & so easily
transported

Chalcophile
Oxyanion
Alkalis

Oxyanion Metals
B (boron)
Sn+4 (tin)
W+6 (tungsten)

10
2.5
1

Incompatible
Incompatible
Incompatible

-XX
XX

----

Alkalis & Alkali Earths

Ba+2 (barium)
340
Compat in Kspar
XXX
-Cs+ (cesium)
1
Compat in Kspar
XXX
-Li+ (lithium)
13
Compat in FeMag
XXX
-Rb+ (rubidium)
60
Compat in Kspar & Bi
XXX
-Sr (strontium)
360
Compat in Plagio
XXX
-Tl+ (thallium)
0.36
Incompatible
XX
-__________________________________________________________________________
#

Average crustal abundances S.R. Taylor, S.M. McLennan, 1985

Evolution of porphyry hydrothermal system

Main factors controlling metal deposition and mineral alteration
oxidation state of fluid
- control on oxide, sulfate and
sulfide deposition
disproportionation of SO2 with
decreasing T
- largely temperature controlled,
increases ratio of H2S to SO2 and
favors sulfide deposition [4SO2 +
4H2O ! H2S + 3HSO4 + 3H+]
Interaction of SO2 gas with
plagioclase or mafic silicates
(sulfidation reaction) increases ratio
of H2S to SO2
fluid acidity
- controls alteration patterns, affects
aH2S. Acidity increases (pH lowers)
with deceasing TC as acids
disassociates

Seedorff et al., 2005

host rock composition and external fluid

composition dictates mineral phases
being precipiated

Weis, Driesner & Heinrich, 2012, Science

Common alteration assemblages

Possible Mineral Assemblage

Process / composition

Generitic Term

Kaolinite-montmorillonite ( illite- chlorite)

K, Ca, Mg-metasomatism

Argillic

Andalusite pyrophyllite - kaolinite ( quartz

muscovite / illite)

K, Ca, Mg-metasomatism

Advanced argillic

Chlorite-sercite ( montmorillonite-illite-smectitecalcite-epidote)

K, Ca, Mg-metasomatism

Intermediate argillic

Muscovite (sericite) quartz -pyrite chlorite

K, Na, Ca, Mg-metasomatism

Phyllic / Sericitic

Albite epidote-chlorite-hematite

Na, Ca, Mg-metasomatism

Sodic

K-feldspar biotite-quartz-sericite-albite-anhydriteepidote / actinolite / pyroxene / garnet

K-metasomatism

Potassic / K Silicate
(Calc-postasic)

Biotite K-feldspar-magnetite-quartz-albite-anhydrite

K-metasomatism

Potassic / K Silicate

Garnet-epidote-actinolite-chlorite-carbonate
magnetite-hematite

Ca-, Na-metasomatism

Calc-silicate

Chlorite-epidote-albite carbonate-sericitemontmorillonite-pyrite-hematite

Ca-Mg-metasomatism

Propylitic

Actinolite-chlorite-albite epidote

Ca, Na-metasomatism

Sodic - Calcic

Evolution of porphyry hydrothermal system

Decreasing T increases
dissociation of salts & acids
(K+ and H+ increase
relative to KCl & HCl)
! dissociation of acids
(HSO4-, HCl, H2CO3) leads
to real acidity increase and
sulfide deposition
Important alteration types
Hydrolytic (acidic), H+ = K+
Alkali exchange, Na+ = K+
Precipitation/dissolution, quartz
Oxidation/reduction (S2, O2)
Greater fluid rock interaction
! neutralizes acidity (H )

Depth influence on disproportionation reaction

In(Porphyry(Cu(systems,(most(
of(the(S(is(ini&ally(in(an(
oxidized(form;(SO2(
'
Magma%c'SO2'
dispropor%onates'through'the'
temp'window'from'450'to'350o'
'
4SO2'+'4H2O'='3H2SO4'+'H2S'
'
This'generates'reduced'S'to'ppt'
suldes,'and'acid'that'converts'
feldspar'to'sericite.'
'
Depth constraint on reaction may provide an explanation for abundance or lack
of magnetite in porphyry Cu deposits
J.H. Dilles,
unpublished 2010

After Seedorff et al. (2005)

A,(B(&(D(veins(classica&on(
(Gustafson'&'Hunt,'1975)>>
linking'veins'to'altera%on'
Rela%on'to'Wall>rock'
altera%on'&'ore'
1.'A'apli%c'quartz'veins'
(Cpy''Bn''Mag)'
associated'with'K>silicate'
alta%on'
2.'B'vns'(qtz>MoS2)'with'
centerline,'stable'in'K>
silicate'
3.'D'veins'(Py'or'Cpy>Py'or'
Py>Bn)'with'wall'rock'
destruc%ve'serici%c'
altera%on.'
In'a'given'ppy'intrusion'
center,'A'vns'are'cut'by'B'
veins'cut'by'D'veins'
(Temperature'decrease)'

Altera&on(Selvage(Forma&on>''

Fluid'moves'along'vein'(advec%ve'transport),'and'diuses'into'rock'
in'pore'uid'
Wedge of
hydrothermally
altered rock
forms with time
and advances
Pervasive
alteration =
overlapping
vein selvages
Geiger et al.,2001

Wall'rock,'uid'composi%on,'and'temperature'controls'
which'hydrothermal'mineral'precipitates'

Hydrothermal mineral assemblages and association

300C
Musc(Phen) +
Chl Ksp or
Bi + Ksp
Pyroph (AA)

Log activities of Mg2+/(H+)2

150C
illite + chl kaol
illite + chl Ksp

400C
Ksp-Musc-Bio
Log activities of K+/H+

Feldspar(precipita&on(
the'role'of'cooling'versus'hea%ng'uids'
Alkali exchange KAlSi3O8 + Na+ = NaAlSi3O8 + K+

Silica (Qz) Solubility--All SiO2 is in

solution in condensed fluid (not vapor)
Magmatic Fluids
A-B vein Qtz in hi-T cooling
Dissolution ~450C

Cooling of magmatichydrothermal
potassic alteration

Heating of
circulating connate
or groundwater
sodic alteration

Seedorff et al., 2005

D veins Qtz <400C

Circulating non-mag
fluids
Dissolve silica on heating to
400C
Precipitation of Qtz causes
sealing, so cannot access
high-T areas

K+/Na+

Brines can access up to

~500C

CL image
Butte qz
(Rusk&Reed)

Temperature effects of metal sulfide precipitation

Experiments'in'one>phase'
eld'of'water>NaCl'

Sequence of sulfide minerals

depends upon Fe/Cu ratio in fluid

Cu>Fe>S'

Early hypogene
with high Fe/Cu

300C

Sericitic alteration
removes Fe,
leading to higher
S state in
superposed
minerals

Rock>buered'assemblage'
Qtz>Ksp>Plag>Musc>Py'

Pb+2 + H2S = PbS + 2H+

Arrow in direction
of increased fS2

Explains'peripheral'
geochemical'zoning'and'lack'
of'Pb>Zn'in'porphyry'Cu'core'
Courtesy of
John Dilles

Porphyry intrusion and

hydrothermal evolution

Successive porphyry intrusions rise

to level of neutral buoyance
following breach of carapace of
underlying magma chamber follow
fractures generated by exsolved
fluid
Begins to crystallize, increasing fluid
pressure until exceeds load, leading
to catastrophic fracturing, transitions
to hydrostatic pressures, and
quench crystallization of magma

Porphyry characteristics
Genetic association with porphyritic granitoid rocks that both
are porphyritic have a sugary (micro-aplitic), fine-grained groundmass
are multiphase, most commonly with decreasing phenocryst abundance and size
with decreasing age

Calcalkalic PCD

Calc-alkalic PCD

Hnbd-bt
granodiorite
porphyry, Reko
Diq, Pakistan

Hnbd-bt
granodiorite
Porphyry,
Quellaveco, Peru

Alkalic PCD
Alkalic PCD

Toodoggone*district,*BC*Canada*

Bingham, Utah

Biotite Quartz
Monzonite, North
Parkes, NSW

Biotite syenite
porphyry,
Galore Creek,
BC

Multiple Igneous Events are Associated with Multiple Hydrothermal Events

Porphyry dikes are Accompanied by K-silicate & Sericitic alteration & are
Followed by Sodic-Calcic, Propylitic-Act, & Related Chlorite-Sericite-HematiteMag Cu-Au

Early stage porphyry emplacement, fluids unmix to brine +

vapor; vapor ascends to near-surface

Dilles et al, in revision

Intermediate stage porphyry emplacement, main porphyry

Cu-Mo (-Au) ore stage from central plume exsolved from
magma; entrainment of non-magmatic water on flanks of
system

Dilles et al, in revision

Late stage, deeper-sourced magmatic fluids penetrate hightemperature system at lower temperature; external fluid
traverses through the porphyry Cu deposit

Dilles et al, in revision

Distribu&on(of(altera&on(facies(and(mineral(
assemblages(in(porphyry(Cu(system(

Magmatic to hydrothermal
transitions Collection of volatiles
at tops of porphyry intrusions

Metal-rich volatiles exsolve from the magma during

crystallization

Dilles, Tosdal, Halley, 2011

Examples of magmatic-hydrothermal transition

Examples of magmatic-hydrothermal transition

Growth
direction
Quartz UST with late cpy
Uni-directional solidification textures

Vein'>'dike'

Cpy>Bn>Mag'lled'
pegmatoid'cavity'

Cpy'droplet'

mineral growth from the roof and

walls of a magma body that is
crystallizing downward and inward
Common beneath areas of high grade

Multiple UST

Quartz veins record loss of volatiles upward from

horizons marked by quartz UST layers
Sample oriented
so that quartz
grains in UST
layers are
pointing
downward and
inward

High(temperature(altera&on((K(silicate(and(peripheral(propylli&c(
Regional*and*vein*controlled*

Many veins at top of

sample; few veins at
bottom of sample
Offsetting vein

yers
UST la

Gro

wth

dire
ction

Batu(Hijau((

Circles mark sites of

fluid release events:
earlier in lighter colors,
later in darker colors

Fluids emanate from

below sample

From Garwin, 2000

Lab 3/4 sample MP-B, Mineral Park, Arizona; courtesy of Eric Seedorff

High temperature pervasive K-silicate (potassic)

alteration
Qtz-bt-Ksparbn-cpy

Pakistan

Kspar-bt-mag

British Columbia

Chl after bt-cpy

Papua New
Guinea

Mag-bt-py

Serbia

Early high temperature veins

(not common in shallowly emplaced systems
Early mus + bornite + cpy
Kspar

Valley, Highland Valley,

Canada

Early dark micaceous veins

W/ biot + sericite + Kspar;
Abundant Cp + Mag + Py

Anaconda Dome,
Butte, USA

Early dark micaceous vein

with biot + chlorite +
bornite + cpy + mag

Relincho, Chile

Irregular qtz-bn-mag

High temperature veins

Sheeted quartz-magnetite veins common at tops of porphyry intrusion

A range of type and mineral infill

Sheeted qtz-cpy

Butte USA

Irregular sugary quartz

with K spar halos

Qtz & anh & Kspar vns

Calcic-potassic alteration

Sulfide occurrences
Disseminated

Center line

Sulfide only

Qtz-bt-Ksparbn-cpy

Oyu Tolgoi, Mongolia

Reko Diq,
Pakistan

SW Oyu Tolgoi,
Mongolia

Occur mostly in syenitic and

certain monzonitic porphyry
copper deposits
Calc-silicate minerals and ore
minerals occur in igneous rocks
Mineralogy

Batu Hijau,
Indonesia

K-feldspar
Biotite
Anhydrite
Garnet
Diopside
Actinolite

Early(and(deep(Na(altera&on(
Early'albite'replacement'of'igneous'
feldspar'which'is'then'overprinted'
by'typical'potassic'altera%on'
mineral'assemblages'
Commonly'logged'as'potassic'
altera%on'
Poorly'understood'altera%on'type'
with'proposal'to'be'magma%c'or'
saline'external'uids'
May'be'more'widespread'than'
currently'accepted'

Sericitic (phyllic) alteration H+ metasomatism

Forms at <350-500C (lower temperatures generally require slightly higher
pH, acidic conditions).
Typical assemblage is sericite quartz pyrite chlorite
In mafic rocks where there is a paucity of K in the protolith get replacement
of Na and Ca by H+, but high (Fe+Mg)/K results in abundant chlorite rather
than sericite
Pervasive sericite-pyrite-qtz, Red Chris

Pebble,(USA(
Lang*and*Gregory,*2012*

Gregory,*2015*

D-vein, Bethsaida,
Highland Valley

District-scale distribution of hydrolytic alteration

Sericite - chlorite (green sericite)

Transition stage between K-silicate and
sericite alteration
Characterized by intergrown chlorite and
phengitic muscovite (sericite)

Sillitoe, 2010

Simuku, PNG

Advanced argillic alteration (Lithocap environment)

Late(Altera&on(

Typically'developed'in'lithocap'environment,'for'example'quartz>alunite'
epithermal'systems'and'above'porphyry'deposits'
Forms'over'a'wide'temperature'range;'<100>600C'
Acidity'of'uids'is'key'control'on'altera%on'
Dominated'by'quartz'plus'combina%ons'of'pyrophyllite,'dickite,'kaolinite,'
alunite,'etc'
Barren lithocap at Cerro Casale, Chile

Barren lithocap at Yerington district, U.S.A

Vertical zoning in PCD system

Leached cap

Veins external to the mineralized porphyry system

Vertically rising buoyant plume cools, creating sericite alteration
immediately above the porphyry, overlain by advanced argillic
Late D-style veins can escape laterally, traveling up to 5 km, and
at Butte up to 10 km laterally

PCD

The most widespread and common selvage minerals are

sericite or fine-grained muscovite replacements of feldspar and
mafics, and chlorite replacements of mafic minerals. Chlorite
occurs in upper and outer exposures of the HT alteration zones
and where mafic content of rock increases.
At shallow depths above porphyry system, specularite may be
present due to the lack of sulfur in the hydrothermal fluid

Fluid saturated carapace

Lateral D-vein form

swarms or discrete veins,
sometimes only mm thick,
and can be mineralized

Vertical, concentric D vein selvages at Ann-Mason, Yerington, Nevada (USA)

Shallow
(<1 km depth)

Courtesy of
John Dilles

Deep, Ore
Zone

Note, in the S-poor and upper parts of the system, specular hematite is stable
in the SC zones, and locally in the S zones rather than pyrite

42

At transition to advanced argillic;

quartz replaces wall rock adjacent to
fluid channel

Sericite-advanced argillic transition

Central quartz vein is rare in the

sericite zone; most of alteration is
conversion of rock to white mica;
phengitic muscovite at depth but
muscovite at shallower levels

CATCHPOLE ET AL.

Central Morococha district:

mine level 400 - 4375 m.a.s.l.
N-8719000

Manto Italia

Ag - Pb

Sierra Nevada

Brecha Rosita

Montero basalt
Duvaz

Zn-Pb-Ag
Huamachuco

Codiciada
composite
stock

Zn - Cu
Riqueza 100 ore body

N-8718000 Ombla,

Brecha Riqueza

Ombla,
upper

lower

Cu
Sulfurosa
pyrite bodies

Gertrudis
porphyry

Legend

San Francisco
porphyry

Toromocho

Churruca

Sulfurosa

Rectificadora

San Francisco

N-8717000

E-375000

fluid inclusion
sample location
base metal vein
massive base metal
mineralization
massive pyrite
replacement bodies

?
Toromocho
composite
stock

View to the San Francisco porphyry

center, Morococha district

0.5 Km

E-377000

Triassic-Jurassic Pucar carbonate rocks

0
Triassic Mitu volcanic rocks

1 km

SSW
Anticona
intrusion

Anticona
intrusion

Manuelita

Codiciada
composite stock

2
3
6
1

Lithologies

Sericite

Sericite

NNE

4800 m

E-378000

N-8716000

E-376000

porphyry intrusions
(dioritic - granodioritic)
Triassic-Jurassic Pucar
carbonate rocks, skarn

quartz feldspar porphyry

Toromocho
pipe breccia
composite
porphyry intrusions
stock
(dioritic - granodioritic)
?
Anticona diorite
Triassic-Jurassic Pucar carbonate rocks, skarn
Jurassic Montero basalt
Triassic-Jurassic Pucar carbonate rocks, silicified
Triassic-Jurassic Pucar carbonate rocks
Triassic Mitu volcanic rocks

4375 m

5
1

Lateral'to'many'but'not'all'
porphyry'Cu'centers'are'zoned'
intermediate'temperature'veins.'
'
These'are'D>type'veins'with'
hydroly%c'altera%on'of'wall'
rocks'
'

2
6

base metal sulfide bodies

pyrite-quartz bodies
1 porphyry-type mineralization
2 contact skarn
3 pyrite bodies

San Francisco
intrusion

Catchpole'et'al.'2015'

4 skarn-hosted sulfide bodies (Manto Italia)

4000 m

5 tube-like replacement bodies

6 Cordilleran polymetallic veins

Fig. 2. Geologic map of mining level 400 (4,375 m.a.s.l.) showing the distribution of massive sulfide mineralization (compiled from multiple mining levels) and schematic cross section in the central Morococha district. Compiled from unpublished
geologic maps of the Cerro de Pasco Copper Corp. (19201960), Centromin Peru, Pan American Silver Corp., and Len
Pimentel (2006).

Evolution of porphyry hydrothermal system

Late, low T stage, <~250C (mainly post-ore)
Fluids cool while reacting with host rocks,
Fluids become increasingly rock buffered
H+ in the fluid is consumed in exchange for cations in the rock as the rock passes into
the intermediate argillic alteration (smectite-illite-kaolinite with K-feldspar stable).
Magmatic fluid is generally mixing with an external fluid source
Characterized by stability of K-feldspar; biotite and plagioclase replaced

Intermediate Argillic Alteration

Illite - chlorite over late
porphry, Red Chris

Propyllitic alteration
progressive'hydra%on'(vola%le'addi%on)''
Forms''at'the'same'%me'as'get'high>T'uids'coming'in'core'of'system''
Forms'in'country'rocks''
Interacts'with'High>T'uid'along'margins'of'plume''
Circula%on'of'the'uid'is'driven'by'the'thermal'energy'of'the'causa%ve'batholith'
Characterized'by'combina%on'of'epidote,'albite,'calcite,'pyrite,'chlorite,'illi%c'clay,'and'
at'higher'T'by'abundance'of'epidote'and'ac%nolite''

Kaolinite overprint on
plagioclase outside D
vn, Highland Valley

Illite overprint on
biotite, Reko Diq
Courtesy of David Cooke

Propylitic alteration

Distal alteration from

the thermally driven
circulation
Temperature increase
toward core
Changes include:
1. Mineralogy
increase in epidote; at
depth transition from
epidote to actinolite/
tremolite
2. Chemistry Zn halo
3. Mineral chemistry
(e.g. Fe3+ in epidote)

1 km

From Garwin, 2000

Map from Norman et al, 1991

Na-Ca alteration
Influx of brines into porphyry
system
Removes most elements and
precipitates Na-rich
plagioclase and Ca-bearing
minerals (actinolite at higher
T and epidote at lower T)

Ac/nolite/tremolite*
*albite**epidoteO
chlorite*

Alteration probably not higher

temperature than 400 C

Na-Ca alteration may destroy grade

Aerial Photo of Blue Hill Fault

Block -- the faulted western half of Ann-

View (looking south) of East Jersey (left pit) and Jersey open pits

Mason, Yerington District, Nevada

Magmatic
upflow
Na>Ca'altered'rocks'

Regional
circulation

Buried PCD

Tremolite-albite over
cpy-py veins

Spatially related systems can lead to large overlapping hydrothermal alteration

Hydrothermal alteration distribution of Reko Diq porphyry cluster

Propylitic

Sericitic (phyllic)
1 km

Transitional ser-chl (clay)

4 km

Intense potassic

CN

Superposition of epithermal over porphyry

(telescoping)

Porphyry(Cu(deposits(are(crustal(scale(
magma&c(hydrothermal(systems(

Superposition of higher Cu-containing minerals formed at

lower temperatures (~300C), commonly in veins over older
higher temperature (>400C) hypogene sulfide minerals
associated with K-silicate alteration

Yerington cross-section from Dilles et al. (2000)

Described at Butte (Brimhall, 1979), but recognized as a common feature of

many porphyry Cu-Mo systems (Chuqui, El Salvador, Escondida, Collahuasi)

Formed late in the hydrothermal evolution of porphyry, locally a couple of Ma

after the K-silicate phase (Escondida Padilla-Garza et al., 2001; perhaps
Chuqui Ossandon et al., 2001)

Commonly forms veins characterized by high-sulfidation type minerals

(bornite, chalcocite, covellite)

Usually present in rocks dominated by sericitic (hydrolytic) alteration

Referred to as Cordilleran base-metal lodes in Peru (Bendezu et al., 2009) and

considered by many to be epithermal in character

Sequence of events at Butte

Main(stage(
veins(

Houston et al., in press

Formed two lower

grade (~0.3-0.4% Cu)
centers

66 Ma
64 Ma
65 Ma

Simplified geology of Butte (Rusk et al., 2008)

Dominated by Ksilicate alteration and

extensive EDM type
veins

~62-63 Ma
~350!275C

Houston et al., in press

Area of intense hydrolytic

(muscovite quartz)
alteration formed last, lying
between porphyry centers

Houston et al., in press

Replacement of lower S
state (cpy) minerals by
higher (bn cc cov en)
Leaching and oxidation of
cpy from older PCD inferred
to be source of Cu in high
sulfidation Cu-FeAs sulfides
in Main Stage veins

Associated with pyrite

Fixed available Fe in rock

Main Stage Metal Zoning in East-West long section

(Proffett, 1979, 1999, ms)note intrepretation of 20 tilt to west
Interpretation: deep sericitic alteration zone is feeder to Main Stage

Chuquicamata Cu-Mo
porphyry deposit
Late qtz-enargite-covellitechalcocite-bornite veins
superposed on lower grade
chalcopyrite-borniteK
silicate altered rocks
Early qtz-Mo veins

Pre-Main Stage
Cu-Mo

Complex and probably

superposed hydrothemal
events
Cu veins general NE to NW
strikes (inherited from Pz
fabrics?)
(Lindsay et al, 1995; Ossandon et al., 2001)

enargite

covellite

chalcocite

pyrite

Ossandon et al., 2001

Chuquicamata cross sections

What happened?
Fluid composition
has evolved with
decreasing
temperature,
increased
fluid:rock ratio,
and time to higher
sulfidation state,
thus enhancing
the precipitation of
late bornitechalcocitecovellite-enargite

Ossandon et al., 2001

Sequence of minerals
depends upon Fe/Cu ratio in
fluid
Early hypogene
with high Fe/Cu

Cu>Fe>S'

Telescoping of epithermal on PCD

300C

Sericitic alteration
removes Fe,
leading to higher
S state in
superposed
minerals

Arrow in direction
of increased fS2
Courtesy of
John Dilles

Exhumation brings porphyry

environment closer to surface,
changing physiochemical environment
of ore deposition

However in some deposits the host rocks dictate the hypogene

mineralogy, which may be similar to that characterizing hypogene
upgrading (telescoping)

Reko(Diq(Complex'

Example from Reko Diq, Balochistan, Pakistan

Geology(

Extensive'10'x'10'km,'eroded'volcanic'eld'
with'cluster'of'18'porphyry'Cu>Au'deposits'

Miocene(porphyry(intervals(
"''23.3''22.40.4'Ma'(Tanjeel'+'Saindak)'
"''18.42.5''14.260.19'Ma'Hbl'phase'
"''13.80.2''11.730.04'Ma'Au'rich'phase'
"''11.40.2''10.50.2'Ma'Cu>Au'phase''

Resources((2009)*
H14>15'='4100'Mt'@0.50%Cu'&'0.30g/t'Au'
Tanjeel''='214'Mt'@0.6%'Supergene'Cu'

H-14
Diamond core drilling at Reko Diq, 2009

H-15

Section from Razique, in prep

Supergene modification (oxidation and upgrading)

H-15 sericite-chalcopyrite-covellite

H-15 sericite-pyrite-bornite-covellite

Removes: Cu, Zn, Fe, Mn, K, +/- As, Au

Remaining: Mo, Pb, Ag, Mn, Fe

Argillic alteration
superposed over higher
temperature, which can be
seen texturally preserved
Low temperature conversion
of minerals to acid stable
phases (e.g. K-spar to illite /
kaolinite)
Toquepala, 1976

Commonly confused with sericitic

alteration, the higher temperature alteration
phase

Supergene
Cu & Fe
Chemistry
A) Source-0)Pyrite-rich
rocks
0)Transport by
acids from
pyrite
B) Precipitation
1) Reduction
on pyrite
2) Neutralization on
feldspar

Oxidation

Supergene alteration
accompanied by argillic
alteration.

But, can be distinguished due to presence of

phyllosilicate crystals in the sericite
alteration and lack in the argillic

Supergene enrichment profile

Cuajone, Peru

Post>mineral''
Chuntacalla'Fm.'

Unoxidized'
sericite>
pyrite>
chalcopyrite'

Variation in sulfide character at the Toki cluster, Chile

Post>mineral'Huaylillas'Fm'

Hema%te'oxida%on'of'chalcocite'zone'

Effect of sulfide content

on supergene
enrichment and
oxidation
Higher pyrite produced
better sulfide
enrichment

Supergene'
chalcocite'

Jarosite'+'goethite'
auer'sericite>pyrite'
rock'

Development of oxidation profiles: Cu + Fe + (Mn,Al)

mobility during oxidative destruction of sulfides
Fe+++ + H2O Fe(OH)3 + 3H+(aq)

Fe(OH)3

FeOOH(s) + H2O

Low pyrite leads to in

situ oxidation with little
Cu transport and
upgrading of Cu content
Sulfide content affects acid
generation capacity and
ability to form supergene or
oxide Cu deposit

Rivera et al., 2010

1. Supergene enrichment is a function of pyrite content

2. Low pyrite yields poor enrichment due to low acid
generation capacity
3. High pyrite yields potential for enrichment
4. Enrichment requires somewhat stable erosion / exhumation
5. Semi-arid climate best (e.g. Andes, SW US)
6. Too high of erosion rates and wet climates exhume the
deposits too fast for significant enrichment to form, thus a
mixed sulfide content
7. Mo and Au will be residual in leached cap
8. Au may be enriched to higher grade due simply to mass
removal
digenite Cu9S5

Chalcocite Cu2S

Porphyry Cu deposits have:

1. More or less predictable distribution of alteration
assemblages
2. Alteration assemblages form from the interplay between
exsolved magmatic-hydrothermal fluid and an external
thermally driven fluid
3. Grade correlates with vein density and with sequence of
porphyry intrusions
4. Supergene enrichment enhances the economics of
deposits (most extensive zones probably been found
and mined unfortunately)
5. Represent the prize for base metal companies as the
giant deposits have >100 year mine life

Toquepala, 2005