Porphyry and Epithermal 101 Forma&on(of(a(porphyry(Cu(deposit(–((

interplay*between*magma/c*and*hydrothermal*processes*
Hydrothermal alteration in silicate rocks
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
Modified*from*Dilles,*1987*

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
Magma%c'Fluids:'
•  Exsolved'fluid'is'primarily'H2O;'
•  Cl>'(chloride)'is'dominant'anion'in'most'exsolved'hydrothermal'
fluid,'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 Metal Continental Crustal Behavior in Hydrothermal Complexation
Crea&on(and(destruc&on(of(permeability(
& fluids
Background (ppm)# Silicate Melt Chloride Sulfide
__________________________________________________________________________
Chalcophile Metals Hydrothermal'altera%on'
creates'permeability'
Ag (silver) 0.08 Incompatible XX X
As (arsenic) 1 Incompatible X X
Compatible – can stay in magma Au (gold)
Bi (bismuth)
0.002
0.06
Incompatible
Incompatible
XX
X
XX
X through'hydrofracturing'
Hg (mercury) 0.08 Incompatible X XX
Incompatible – can go into fluid Co (cobalt)
Cr (chromium)
10
140
Compat in Olivine
Compat in FeMag
XX
XX
--
-- and'destroys'permeability'
Many trace elements chloride
Cu (copper)
Mn (manganese)
75
1400
Incompatible
Compat. in FeMags
XXX
XXX
X?
-- through'mineral'
Mo (molybdenum) 1 Incompatible -- --
Ni (nickel) 20 Compat in Olivine XX -- precipita%on.'
complexed, & so easily Pb (lead) 8 Compat. in Feldspar XXX --
Sb (antimony)
Se (selenium)
0.2
0.05
Incompatible
Incompatible
X
X
X?
X?
'
transported Te (tellurium) 0.001 Incompatible X --
Repe%%ve'process'with'
V (vanadium) 190 Compat. In FeMag & Ox XX --
Zn (zinc) 80 Compat. in FeMags XXX --

Chalcophile Oxyanion Metals

repeated'fluid'pulses'
B (boron)
Sn+4 (tin)
10
2.5
Incompatible
Incompatible
--
XX
--
--
'
W+6 (tungsten) 1 Incompatible XX --
External'fluid'interacts'
Oxyanion Alkalis & Alkali Earths
Ba+2 (barium) 340 Compat in Kspar XXX -- with'magma%c>
Cs+ (cesium)
Li+ (lithium)
1
13
Compat in Kspar
Compat in FeMag
XXX
XXX
--
--
hydrothermal'fluid'at'
Alkalis Rb+ (rubidium)
Sr (strontium)
60
360
Compat in Kspar & Bi
Compat in Plagio
XXX
XXX
--
-- interface..''Interac%on'via'
Tl+ (thallium) 0.36 Incompatible XX --
__________________________________________________________________________ altera%on'mineralogy'
#
Average crustal abundances S.R. Taylor, S.M. McLennan, 1985 Weis, Driesner & Heinrich, 2012, Science

Evolution of porphyry hydrothermal system

Common alteration assemblages
Main factors controlling metal deposition and mineral alteration
•  oxidation state of fluid Possible Mineral Assemblage Process / composition Generitic Term
- control on oxide, sulfate and Kaolinite-montmorillonite (± illite- chlorite) K, Ca, Mg-metasomatism Argillic
sulfide deposition
Andalusite – pyrophyllite - kaolinite (± quartz – K, Ca, Mg-metasomatism Advanced argillic
•  disproportionation of SO2 with muscovite / illite)
decreasing T Chlorite-sercite (± montmorillonite-illite-smectite- K, Ca, Mg-metasomatism Intermediate argillic
- largely temperature controlled, calcite-epidote)

increases ratio of H2S to SO2 and Muscovite (sericite) – quartz -pyrite ± chlorite K, Na, Ca, Mg-metasomatism Phyllic / Sericitic

favors sulfide deposition [4SO2 + Albite ± epidote-chlorite-hematite Na, Ca, Mg-metasomatism Sodic
-
4H2O ! H2S + 3HSO4 + 3H+]
K-feldspar ± biotite-quartz-sericite-albite-anhydrite- K-metasomatism Potassic / K Silicate
•  Interaction of SO2 gas with epidote / actinolite / pyroxene / garnet (Calc-postasic)
plagioclase or mafic silicates Biotite ± K-feldspar-magnetite-quartz-albite-anhydrite K-metasomatism Potassic / K Silicate
(sulfidation reaction) increases ratio
Garnet-epidote-actinolite-chlorite-carbonate ± Ca-, Na-metasomatism Calc-silicate
of H2S to SO2 magnetite-hematite
Seedorff et al., 2005
•  fluid acidity Chlorite-epidote-albite ± carbonate-sericite- Ca-Mg-metasomatism Propylitic
•  host rock composition and external fluid montmorillonite-pyrite-hematite
- controls alteration patterns, affects
aH2S. Acidity increases (pH lowers) composition – dictates mineral phases Actinolite-chlorite-albite ± epidote Ca, Na-metasomatism Sodic - Calcic

with deceasing T°C as acids being precipiated

disassociates

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 )
After Seedorff et al. (2005)
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'
sulfides,'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

A,(B(&(D(veins(classifica&on( Altera&on(Selvage(Forma&on>''
(Gustafson'&'Hunt,'1975)>> Fluid'moves'along'vein'(advec%ve'transport),'and'diffuses'into'rock'
linking'veins'to'altera%on'
in'pore'fluid'
Rela%on'to'Wall>rock'
altera%on'&'ore' •  Wedge of
1.'‘A’'apli%c'quartz'veins' hydrothermally
(Cpy'±'Bn'±'Mag)' altered rock
associated'with'K>silicate' forms with time
alta%on'
and advances
2.'‘B’'vns'(qtz>MoS2)'with'
centerline,'stable'in'K>
silicate' •  Pervasive
3.'‘D’'veins'(Py'or'Cpy>Py'or' alteration =
Py>Bn)'with'wall'rock' overlapping
destruc%ve'serici%c'
altera%on.' vein selvages
In'a'given'ppy'intrusion'
center,'A'vns'are'cut'by'B' Geiger et al.,2001
veins'cut'by'D'veins'
(Temperature'decrease)'
 Wall'rock,'fluid'composi%on,'and'temperature'controls' Hydrothermal mineral assemblages and association
which'hydrothermal'mineral'precipitates'

•  150°C
•  illite + chl ± kaol
•  illite + chl ± Ksp

•  300°C Log activities of Mg2+/(H+)2

•  Musc(Phen) +
Chl ± Ksp or
•  Bi + Ksp
•  Pyroph (AA)

•  400°C
•  Ksp-Musc-Bio

Log activities of K+/H+ Seedorff et al., 2005

Feldspar(precipita&on( Silica (Qz) Solubility--All SiO2 is in

the'role'of'cooling'versus'hea%ng'fluids' solution in condensed fluid (not vapor)
Magmatic Fluids CL image
•  Alkali exchange KAlSi3O8 + Na+ = NaAlSi3O8 + K+ Butte qz
A-B vein Qtz in hi-T cooling (Rusk&Reed)
Dissolution ~450°C
Cooling of magmatic-
hydrothermal — D veins Qtz <400°C
potassic alteration Circulating non-mag
fluids
Dissolve silica on heating to
400°C
Heating of
Precipitation of Qtz causes
circulating connate sealing, so cannot access
or groundwater — high-T areas
sodic alteration K+/Na+ Brines can access up to
~500°C
 Sequence of sulfide minerals
Temperature effects of metal sulfide precipitation
depends upon Fe/Cu ratio in fluid Cu>Fe>S'
•  Early hypogene
with high Fe/Cu
Experiments'in'one>phase' 300°C
field'of'water>NaCl' •  Sericitic alteration
removes Fe,
leading to higher
Rock>buffered'assemblage' S state in
Qtz>Ksp>Plag>Musc>Py' superposed
minerals

Pb+2 + H2S = PbS + 2H+

Explains'peripheral' Arrow in direction

geochemical'zoning'and'lack' of increased fS2
of'Pb>Zn'in'porphyry'Cu'core'
Courtesy of
John Dilles

Porphyry intrusion and Successive porphyry intrusions rise

hydrothermal evolution
Porphyry characteristics
to level of neutral buoyance
following breach of carapace of •  Genetic association with porphyritic granitoid rocks that both
underlying magma chamber – follow
–  are porphyritic have a sugary (micro-aplitic), fine-grained groundmass
fractures generated by exsolved
fluid –  are multiphase, most commonly with decreasing phenocryst abundance and size
with decreasing age
Begins to crystallize, increasing fluid
pressure until exceeds load, leading
to catastrophic fracturing, transitions Alkalic PCD
Calcalkalic PCD Calc-alkalic PCD
to hydrostatic pressures, and Alkalic PCD
quench crystallization of magma

Toodoggone*district,*BC*Canada*

Hnbd-bt Hnbd-bt Biotite syenite

granodiorite granodiorite Biotite Quartz porphyry,
porphyry, Reko Porphyry, Monzonite, North Galore Creek,
Bingham, Utah Diq, Pakistan Quellaveco, Peru Parkes, NSW BC
 Multiple Igneous Events are Associated with Multiple Hydrothermal Events
Porphyry dikes are Accompanied by K-silicate & Sericitic alteration & are Early stage porphyry emplacement, fluids unmix to brine +
Followed by Sodic-Calcic, Propylitic-Act, & Related Chlorite-Sericite-Hematite±Mag ± Cu-Au
vapor; vapor ascends to near-surface

Dilles et al, in revision

Intermediate stage porphyry emplacement, main porphyry Late stage, deeper-sourced magmatic fluids penetrate high-
Cu-Mo (-Au) ore stage from central plume exsolved from temperature system at lower temperature; external fluid
magma; entrainment of non-magmatic water on flanks of traverses through the porphyry Cu deposit
system

Dilles et al, in revision Dilles et al, in revision

Distribu&on(of(altera&on(facies(and(mineral( Magmatic to hydrothermal
assemblages(in(porphyry(Cu(system( transitions — Collection of volatiles
at tops of porphyry intrusions

Metal-rich volatiles exsolve from the magma during

Dilles, Tosdal, Halley, 2011 crystallization

Examples of magmatic-hydrothermal transition Examples of magmatic-hydrothermal transition

Growth
direction

Quartz UST with late cpy

Uni-directional solidification textures

•  mineral growth from the roof and Multiple UST

walls of a magma body that is
crystallizing downward and inward
Vein'>'dike' Cpy>Bn>Mag'filled' Cpy'droplet'
pegmatoid'cavity'
•  Common beneath areas of high grade
 Quartz veins record loss of volatiles upward from High(temperature(altera&on(–(K(silicate(and(peripheral(propylli&c(
horizons marked by quartz UST layers Regional*and*vein*controlled*

Sample oriented
so that quartz Many veins at top of
grains in UST sample; few veins at
layers are bottom of sample
pointing
downward and Offsetting vein
inward
yers
UST la Gro
wth
dire Batu(Hijau((
ction

Circles mark sites of

Fluids emanate from fluid release events:
below sample earlier in lighter colors,
later in darker colors
From Garwin, 2000
Lab 3/4 sample MP-B, Mineral Park, Arizona; courtesy of Eric Seedorff

High temperature pervasive K-silicate (potassic) Early high temperature veins

(not common in shallowly emplaced systems
alteration
Early dark micaceous veins Early dark micaceous vein
Kspar-bt-mag Chl after bt-cpy Mag-bt-py Early mus + bornite + cpy
Qtz-bt-Kspar- W/ biot + sericite + Kspar; with biot + chlorite +
bn-cpy ± Kspar Abundant Cp + Mag + Py bornite + cpy + mag

Papua New
Pakistan British Columbia Guinea Serbia
Valley, Highland Valley, Anaconda Dome,
Canada Butte, USA 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

Sulfide occurrences Calcic-potassic alteration

•  Occur mostly in syenitic and
Disseminated Center line Sulfide only certain monzonitic porphyry
copper deposits
Qtz-bt-Kspar-
bn-cpy •  Calc-silicate minerals and ore
minerals occur in igneous rocks
•  Mineralogy
–  K-feldspar
–  Biotite
–  Anhydrite
–  Garnet
Oyu Tolgoi, Mongolia –  Diopside
–  Actinolite

Reko Diq, Batu Hijau,

SW Oyu Tolgoi,
Pakistan Indonesia
Mongolia
 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'fluids'
•  May'be'more'widespread'than'
currently'accepted'
Pebble,(USA(
Lang*and*Gregory,*2012* Gregory,*2015*
District-scale distribution of hydrolytic alteration
Sericitic (phyllic) alteration — H+ metasomatism
•  Forms at <350-500°C (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
D-vein, Bethsaida,
Highland Valley
Sericite - chlorite (green sericite)
Transition stage between K-silicate and
sericite alteration
Characterized by intergrown chlorite and
phengitic muscovite (sericite)
Simuku, PNG
Sillitoe, 2010
 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>600°C'
•  Acidity'of'fluids'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

Veins external to the mineralized porphyry system
Leached cap
•  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

Vertical, concentric D vein selvages at Ann-Mason, Yerington, Nevada (USA) Lateral D-vein form
swarms or discrete veins,
Shallow sometimes only mm thick,
(<1 km depth)
and can be mineralized

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 CATCHPOLE ET AL.

Central Morococha district: B

At transition to advanced argillic; mine level 400 - 4375 m.a.s.l. Manto Italia

Lateral'to'many'but'not'all'
N-8719000 Sierra Nevada

quartz replaces wall rock adjacent to Ag - Pb Brecha Rosita

porphyry'Cu'centers'are'zoned'
Montero basalt
fluid channel Zn-Pb-Ag
Duvaz

intermediate'temperature'veins.'
Huamachuco

Central quartz vein is rare in the Zn - Cu

? Codiciada
composite

'
stock
sericite zone; most of alteration is
Riqueza 100 ore body

N-8718000 Ombla, Brecha Riqueza

Ombla,
lower upper

conversion of rock to white mica; These'are'D>type'veins'with'

Cu
Sulfurosa
pyrite bodies

phengitic muscovite at depth but

hydroly%c'altera%on'of'wall'
Gertrudis
porphyry
San Francisco
muscovite at shallower levels porphyry

rocks'
Toromocho
Churruca
Sulfurosa
Sericite-advanced argillic transition Legend N-8717000
Rectificadora

San Francisco

'
E-375000
fluid inclusion
sample location ?
base metal vein
massive base metal
mineralization Toromocho
massive pyrite composite
replacement bodies
porphyry intrusions
stock
View to the San Francisco porphyry
A ?
(dioritic - granodioritic)
Triassic-Jurassic Pucará
center, Morococha district
carbonate rocks, skarn N-8716000
?

E-376000

E-378000
E-377000
Triassic-Jurassic Pucará carbonate rocks
Triassic Mitu volcanic rocks
0 0.5 Km
Manuelita

1 km Codiciada
SSW composite stock NNE
4800 m
Anticona
1
intrusion
Anticona
intrusion 2

1 3

A 1 4
B
Lithologies 5
4375 m
quartz feldspar porphyry 2 base metal sulfide bodies
Toromocho 1
pipe breccia 6 pyrite-quartz bodies
composite
porphyry intrusions 1 porphyry-type mineralization
stock
(dioritic - granodioritic)
Anticona diorite ? 2 contact skarn
Triassic-Jurassic Pucará carbonate rocks, skarn 3 3 pyrite bodies
Jurassic Montero basalt San Francisco 4 skarn-hosted sulfide bodies (Manto Italia)

Sericite Sericite
Triassic-Jurassic Pucará carbonate rocks, silicified
Triassic-Jurassic Pucará carbonate rocks
intrusion 4000 m 5 tube-like replacement bodies
6 Cordilleran polymetallic veins
Triassic Mitu volcanic rocks
Catchpole'et'al.'2015'
Fig. 2. Geologic map of mining level 400 (4,375 m.a.s.l.) showing the distribution of massive sulfide mineralization (com-
piled 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. (1920–1960), Centromin Peru, Pan American Silver Corp., and León
Pimentel (2006).
 Evolution of porphyry hydrothermal system
Late, low T stage, <~250°C (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 Propyllitic alteration

Illite - chlorite over late
porphry, Red Chris
progressive'hydra%on'(vola%le'addi%on)''
•  Forms''at'the'same'%me'as'get'high>T'fluids'coming'in'core'of'system''
•  Forms'in'country'rocks''
•  Interacts'with'High>T'fluid'along'margins'of'plume''
•  Circula%on'of'the'fluid'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
1 km
From Garwin, 2000 (e.g. Fe3+ in epidote)
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 Ac/nolite/tremolite*
minerals (actinolite at higher –*albite*±*epidoteO
T and epidote at lower T) chlorite*

Alteration probably not higher

temperature than 400° C

Na-Ca alteration may destroy grade

 Aerial Photo of Blue Hill Fault
View (looking south) of East Jersey (left pit) and Jersey open pits Block -- the faulted western half of Ann-
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 CN

Intense potassic
 Porphyry(Cu(deposits(are(crustal(scale( Superposition of epithermal over porphyry
magma&c(hydrothermal(systems( (telescoping)
Superposition of higher Cu-containing minerals formed at
lower temperatures (~300±°C), commonly in veins over older
higher temperature (>400°C) hypogene sulfide minerals
associated with K-silicate alteration

•  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

Yerington cross-section from Dilles et al. (2000) considered by many to be “epithermal” in character

Sequence of events at Butte

Main(stage(
veins(

Houston et al., in press

66 Ma
•  Formed two lower
grade (~0.3-0.4% Cu)
centers
64 Ma
•  Dominated by K-
65 Ma
silicate alteration and
extensive EDM type
veins
Simplified geology of Butte (Rusk et al., 2008)
 ~62-63 Ma
~350°!275°C

Houston et al., in press Houston et al., in press

•  Area of intense hydrolytic •  Replacement of lower S
(muscovite – quartz) enargite
state (cpy) minerals by chalcocite
alteration formed last, lying higher (bn – cc – cov – en)
between porphyry centers
•  Leaching and oxidation of
•  Associated with pyrite cpy from older PCD inferred
to be source of Cu in high
•  Fixed available Fe in rock sulfidation Cu-Fe±As sulfides covellite pyrite
in Main Stage veins

Chuquicamata Cu-Mo Ossandon et al., 2001

Main Stage Metal Zoning in East-West long section porphyry deposit
(Proffett, 1979, 1999, ms)—note intrepretation of 20° tilt to west
Interpretation: deep sericitic alteration zone is feeder to Main Stage
Late qtz-enargite-covellite-
chalcocite-bornite veins
superposed on lower grade
chalcopyrite-bornite±K
silicate altered rocks
Early qtz-Mo veins
Complex and probably
Pre-Main Stage superposed hydrothemal
Cu-Mo events
Cu veins general NE to NW
strikes (inherited from Pz
fabrics?)
(Lindsay et al, 1995; 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 bornite-
chalcocite-
covellite-enargite

Ossandon et al., 2001

Telescoping of epithermal on PCD

Sequence of minerals Cu>Fe>S'
depends upon Fe/Cu ratio in
fluid
300°C
•  Early hypogene
with high Fe/Cu

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

Arrow in direction
Exhumation brings porphyry
of increased fS2 environment closer to surface,
changing physiochemical environment
Courtesy of
John Dilles
of ore deposition
 However in some deposits the host rocks dictate the hypogene Example from Reko Diq, Balochistan, Pakistan
mineralogy, which may be similar to that characterizing hypogene
upgrading (telescoping)
Geology(
Reko(Diq(Complex' Extensive'10'x'10'km,'eroded'volcanic'field'
with'cluster'of'18'porphyry'Cu>Au'deposits'

Miocene(porphyry(intervals(
" ''23.3'–'22.4±0.4'Ma'(Tanjeel'+'Saindak)'
" ''18.4±2.5'–'14.26±0.19'Ma'Hbl'phase'
" ''13.8±0.2'–'11.73±0.04'Ma'Au'rich'phase'
" ''11.4±0.2'–'10.5±0.2'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-15
H-14

Diamond core drilling at Reko Diq, 2009

Section from Razique, in prep

Supergene modification (oxidation and upgrading)

H-15 – sericite-chalcopyrite-covellite

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

Remaining: Mo, Pb, Ag, Mn, Fe
H-15 – sericite-pyrite-bornite-covellite
 Supergene alteration
Supergene
accompanied by argillic
alteration. Cu & Fe
Chemistry
Argillic alteration
superposed over higher A) Source--
temperature, which can be

Oxidation
0)Pyrite-rich
seen texturally preserved rocks
0)Transport by
Low temperature conversion acids from
of minerals to acid stable pyrite
phases (e.g. K-spar to illite / B) Precipitation
kaolinite) 1) Reduction
on pyrite
Toquepala, 1976 2) Neutra-
Commonly confused with sericitic lization on
alteration, the higher temperature alteration feldspar
phase
But, can be distinguished due to presence of
phyllosilicate crystals in the sericite
alteration and lack in the argillic

Supergene enrichment profile Variation in sulfide character at the Toki cluster, Chile
Cuajone, Peru Effect of sulfide content
Post>mineral'Huaylillas'Fm'
on supergene
enrichment and
Post>mineral'' Hema%te'oxida%on'of'chalcocite'zone'
oxidation
Chuntacalla'Fm.'
Higher pyrite produced
better sulfide
enrichment
Low pyrite leads to in
Supergene' Jarosite'+'goethite'
Unoxidized'
chalcocite' situ oxidation with little
sericite> auer'sericite>pyrite'
rock' Cu transport and
pyrite>
chalcopyrite' upgrading of Cu content
Sulfide content affects acid
Development of oxidation profiles: Cu + Fe + (Mn,Al) generation capacity and
mobility during oxidative destruction of sulfides ability to form supergene or
Fe+++ + H2O → Fe(OH)3 + 3H+(aq) Fe(OH)3 → FeOOH(s) + H2O 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