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Forma&on(of(a(porphyry(Cu(deposit(((
interplay*between*magma/c*and*hydrothermal*processes*
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).'''
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'
Chalcophile
Oxyanion
Alkalis
Oxyanion Metals
B (boron)
Sn+4 (tin)
W+6 (tungsten)
10
2.5
1
Incompatible
Incompatible
Incompatible
-XX
XX
----
Process / composition
Generitic Term
K, Ca, Mg-metasomatism
Argillic
K, Ca, Mg-metasomatism
Advanced argillic
Chlorite-sercite ( montmorillonite-illite-smectitecalcite-epidote)
K, Ca, Mg-metasomatism
Intermediate argillic
Phyllic / Sericitic
Albite epidote-chlorite-hematite
Sodic
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
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'
300C
Musc(Phen) +
Chl Ksp or
Bi + Ksp
Pyroph (AA)
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+
Cooling of magmatichydrothermal
potassic alteration
Heating of
circulating connate
or groundwater
sodic alteration
Circulating non-mag
fluids
Dissolve silica on heating to
400C
Precipitation of Qtz causes
sealing, so cannot access
high-T areas
K+/Na+
CL image
Butte qz
(Rusk&Reed)
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'
Arrow in direction
of increased fS2
Explains'peripheral'
geochemical'zoning'and'lack'
of'Pb>Zn'in'porphyry'Cu'core'
Courtesy of
John Dilles
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
Late stage, deeper-sourced magmatic fluids penetrate hightemperature system at lower temperature; external fluid
traverses through the porphyry Cu deposit
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
Growth
direction
Quartz UST with late cpy
Uni-directional solidification textures
Vein'>'dike'
Cpy>Bn>Mag'lled'
pegmatoid'cavity'
Cpy'droplet'
Multiple UST
High(temperature(altera&on((K(silicate(and(peripheral(propylli&c(
Regional*and*vein*controlled*
yers
UST la
Gro
wth
dire
ction
Batu(Hijau((
Lab 3/4 sample MP-B, Mineral Park, Arizona; courtesy of Eric Seedorff
Pakistan
Kspar-bt-mag
British Columbia
Papua New
Guinea
Mag-bt-py
Serbia
Anaconda Dome,
Butte, USA
Relincho, Chile
Irregular qtz-bn-mag
Sheeted qtz-cpy
Butte USA
Calcic-potassic alteration
Sulfide occurrences
Disseminated
Center line
Sulfide only
Qtz-bt-Ksparbn-cpy
Reko Diq,
Pakistan
SW Oyu Tolgoi,
Mongolia
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'
Pebble,(USA(
Lang*and*Gregory,*2012*
Gregory,*2015*
D-vein, Bethsaida,
Highland Valley
Sillitoe, 2010
Simuku, PNG
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
PCD
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.
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
0.5 Km
E-377000
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
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
San Francisco
intrusion
Catchpole'et'al.'2015'
4000 m
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).
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
1 km
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*
View (looking south) of East Jersey (left pit) and Jersey open pits
Magmatic
upflow
Na>Ca'altered'rocks'
Regional
circulation
Buried PCD
Tremolite-albite over
cpy-py veins
Propylitic
Sericitic (phyllic)
1 km
Intense potassic
CN
Porphyry(Cu(deposits(are(crustal(scale(
magma&c(hydrothermal(systems(
Main(stage(
veins(
66 Ma
64 Ma
65 Ma
~62-63 Ma
~350!275C
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
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
enargite
covellite
chalcocite
pyrite
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
Sequence of minerals
depends upon Fe/Cu ratio in
fluid
Early hypogene
with high Fe/Cu
Cu>Fe>S'
300C
Sericitic alteration
removes Fe,
leading to higher
S state in
superposed
minerals
Arrow in direction
of increased fS2
Courtesy of
John Dilles
Reko(Diq(Complex'
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
H-15 sericite-chalcopyrite-covellite
H-15 sericite-pyrite-bornite-covellite
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
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.
Post>mineral''
Chuntacalla'Fm.'
Unoxidized'
sericite>
pyrite>
chalcopyrite'
Hema%te'oxida%on'of'chalcocite'zone'
Supergene'
chalcocite'
Jarosite'+'goethite'
auer'sericite>pyrite'
rock'
Fe(OH)3
FeOOH(s) + H2O
Chalcocite Cu2S
Toquepala, 2005