Geochemical and Mineralogical

Footprints of porphyry Cu-Au deposits

Scott Halley

January, 2016
Why are there acid zones on top of
porphyry Cu systems?

Between 450 and 350, SO2 is

converted to H2S.

4SO2 + 4H2O = H2S + 3H2SO4

This creates lots of acid. In the spent

fluid plume above the porphyry, the
H2S generated from the SO2 produces
pyrite, and the accompanying acid
produces sericite. In the center of the
outflow systems where the acid is
most intense, advanced argillic
assemblages may be formed.
 Alteration Diagram

Temperature versus acidity.

Going down temperature,

reactions follow the mineral
boundaries until one of the acid-
Decreasing buffering components is
temperature completely replaced

Increasing
acidity
 Rock chip Bismuth assays.
Bismuth also maps the phyllic haloes around the 3 porphyry centres.

1 km
 Rock chip Manganese assays.
As alteration breaks down amphiboles, divalent cations from the amphibole go into solution and are depleted. These metals
include Zn, Mn, Co, Ni (even Cu is depleted in most of the phyllic environment).

1 km
 Rock chip Zn, Mn, Ni, Co assays.
Probability plots show the depletion of the Fe-Mg-silicate-hosted divalent transition metal cations relative to the alteration
mineralogy.
 Rock chip Copper assays.
A cumulative frequency plot shows that copper is also depleted throughout most of the phyllic alteration plume above the
porphyry deposits!
Bismuth plotted relative to Sodium-depletion footprint.
Manganese plotted relative to Sodium-depletion footprint.
 Contrasting behaviour of chloride-complexing versus
oxygen-complexing metals

0
A n io n s ( - 1 /- 2 ) a n d
o x y a n io n s ( + 5 / + 6 )

-2
A s5+ Sb 5+
B i5+ W 6+
M o 6+

H y d r o x id e , o x id e s
-4 A g+ C u 2+
Pb 2+
Zn 2+
a n d h a lid e s ( + 3 /+ 4 )
S o l u b ili t y
l o g ( M t o t a l)
C a t io n s ( + 1 /+ 2 )
-6 -
A u C l4

A u ( S 2 O 3 ) 2-
-8
3+
A u A l3+ F e 3+
Si4+
-1 0 A c id A lk a lin e

N a tura l p H ra n ge
-1 2
2 4 6 8 10 12
pH
L M L s 0 3 0 -9 9
L. Law rance
 Metal deposition environments

Cu
Mo
Bi
Decreasing Te Mn
temperature
As Zn
Sb Pb
Hg Ag
Tl

Increasing
acidity
Tl>2ppm

Sb>5ppm

As>50ppm

Bi, Te>1ppm

Sn>5ppm

Mo>5ppm
Porphyry Cu
mineralization
Tl>2ppm

Sb>5ppm

As>50ppm

Bi, Te>1ppm

Sn>5ppm

Mo>5ppm
Porphyry Cu
mineralization
In Porphyry Cu systems, most
of the S is initially in an
oxidized form; SO2

Magmatic SO2 disproportionates

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.
 In Porphyry Cu systems, most
SO2 << H2S of the S is initially in an
oxidized form; SO2

Magmatic SO2 disproportionates

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.

SO2 >> H2S

 Pyrite

As magmatic hydrothermal
fluids cool, SO2 is converted to
H2S .

Chalcopyrite + Pyrite The Cu/Fe/S/O mineralogy pattern

is governed by the SO2 to H2S ratio

Porphyries are most oxidised at

the bottom;
Chalcopyrite
As the SO2 to H2S ratio decreases,
the mineralogy changes from
magnetite to bornite to
Bornite chalcopyrite to pyrite.
 North-South Cross Section through Ann-Mason Deposit

• View is Same as Jurassic Plan Map

• >495 M Tons @0.4% Cu (= 2 M T),

~50 g/t Mo ~0.5 g/t Ag (depth open)
•Alteration-sulfides are centered on
plug of Luhr Hill granite and granite
porphyry dike swarm
• Highest Cu grades correspond to
K-silicate (Biot±Ksp) with Bn-Cp
or Cp dominant
• Late sodic (albite) alteration probably
removed Cu from core of deposit
• Sericitic (D veins with sericite
selvages) occur in periphery along
steeply north-dipping structures,
with Py>>Cp

Modified from Dilles & Einaudi, 1992

Future discoveries are likely to be blind at surface.
Deposits hidden by barren fresh rock, transported cover
or metal-depleted regolith.

What is the “spent fluid” signature

above a blind deposit?

Seedorff et al., 2005

Future discoveries are likely to be blind at surface.

What drill spacing is required to

identify the footprint of a porphyry
system beneath transported cover?

Seedorff et al., 2005

Future discoveries are likely to be blind at surface.

If copper is depleted at surface,

Depleted saprolite. what other signatures might be
preserved in the depleted
saprolite?

Seedorff et al., 2005

Geochemical Exploration Strategy

Pick a sample medium that is appropriate for

the environment;
• Rock chips
• Soils
• Base-of-slope fines
• Bedrock RAB (under cover)

Use a BROAD spaced sampling pattern to

identify the footprint of the system.

Use multielement geochemistry to map the

zoning in the system;
• In fresh rocks use major elements to quantify
the mineralogy
• In weathered media, use metal zoning as a
proxy for the alteration zone.

Understand how saprolitic weathering

remobilizes metals!!!
 Design Scatterplots that display the
stoichiometry of the alteration minerals
Feldspar-Sericite K/Al vs Na/Al Molar ratio Plot
Orthoclase
K/Al (Molar)

Phyllic Potassic
Muscovite
Illite

Albite
Argillic

Kaolinite, Montmorillonite Na/Al (Molar)

Potassic Alteration

Biotite replacing Hbl, Karakatel, Turkey

Weak Phyllic Alteration

Sericite selvedge to Qyz-Py vein, Anne Mason, Nevada

Strong Phyllic Alteration

Sericite-chlorite-pyrite, Anne Mason, Nevada

Advanced Argillic Alteration
Pyrophyllite, dickite, alunite

Pyrophyllite-Alunite, Puren Sur, Chile

Intermediate Argillic Alteration

Illite-Smectite, Zaldivar, Chile

Intermediate Argillic Alteration

Kaolinite overprinting potassic alteration,

Red Chris, British Columbia
Propylitic Alteration
Sodic-Calcic Alteration

Epidote-albite, Highland Valley, British Columbia

Adularia Alteration

Adularia-Chlorite, Chatree, Thailand

 Case Study; Yerington, Nevada
Mineralogy estimated from multielement geochem
 Case Study; Yerington, Nevada
Mineralogy estimated from multielement geochem

Feldspar-Sericite K/Al vs Na/Al Molar ratio Plot

Mineralogy, Anne Mason, Yerington Nevada

Anne Mason orebody

Singatse Fault
 Case Study; Yerington, Nevada
Mineralogy estimated from multielement geochem
 Case Study; Yerington, Nevada
Pathfinders versus Mineralogy

Metals that are soluble as oxyanion complexes are

enriched within zones of acid alteration.
Case Study; Yerington, Nevada
Pathfinder patterns
 Case Study; Yerington, Nevada
Pathfinders versus Mineralogy

Metals that are soluble as oxyanion complexes are

enriched within zones of acid alteration.
Case Study; Yerington, Nevada
Pathfinder patterns
 Case Study; Yerington, Nevada
Pathfinders versus Mineralogy

Metals that are soluble as chloride complexes are depleted within

zones of acid alteration.
Case Study; Yerington, Nevada
Pathfinder patterns
Soil Geochemistry over a blind Porphyry Copper deposit
Copper
Soil Geochemistry over a blind Porphyry Copper deposit
Molybdenum
Soil Geochemistry over a blind Porphyry Copper deposit
Bismuth
Soil Geochemistry over a blind Porphyry Copper deposit
Selenium
Soil Geochemistry over a blind Porphyry Copper deposit
Tellurium
 Supergene leaching of metal patterns.

0
In acid weathering environments,
A n io n s ( - 1 /- 2 ) a n d
o x y a n io n s ( + 5 /+ 6 ) metals that form chloride
-2
A s5+ Sb 5+
B i5+ W 6+
M o 6+
complexes are DEPLETED in the
H y d r o x i d e , o x id e s
A g+ C u a n d h a lid e s ( + 3 / + 4weathering profile;
2+ 2+ 2+
-4 Pb Zn )

C a t io n s ( + 1 / + 2 ) •
S o l u b il it y
lo g ( M t o t a l )
-6
Cu, Au, Ag, Zn, Pb
-
A uC l4

A u ( S 2 O 3 ) 2-
-8
3+
Metals that form oxyanion
A u A l3+ F e 3+
Si 4+
-1 0 A c id A lk a li n e
complexes are relatively immobile,
-1 2
N a tura l p H ra n ge or supergene enriched right
L M L s 0 30 -99
2 4 6
pH
8 10 12
L. Law rance
through the oxide zone
• Mo, Bi, Te, As, Sb, Tl, Sn, W, etc

• We can still map the metal

zonation in very leached profiles
using the oxyanion suite!!!
 Example from an Epithermal System
Zinc Blue<100 ppm, Red > 1000ppm
Zinc is strongly depleted in the saprolite

Post-mineral cover

Base of Oxidation
 Example from an Epithermal System
Gold Blue<0.1 ppm, Red > 1 ppm
Localized supergene enrichment in saprolite

Post-mineral cover

Base of Oxidation

Gold Grades displayed on a long section

Note the two layers of supergene mineralization
 Example from an Epithermal System
Arsenic Blue<50 ppm, Red > 500 ppm
Arsenic enrichment in upper saprolite

Post-mineral cover

Base of Oxidation
Contrasting behaviour of chloride-complexing metals versus
oxyanion-forming metals in a supergene weathered profile

Copper

Molybdenum
Hyperspectral Zonation patterns in PCD’s.

Portable infrared spectrometers are

fast enough to use them as
systematic logging tools.

This removes the subjectivity in

alteration logging.
 Solid solution substitutions in white micas can be
measured indirectly from SWIR spectra.
Sericite Spectrum
FSFR.2187 Int=5.0 sec
1

2112.51

2481.82
0.9

2442.98
0.8
HullQuot

2356.19

2344.8
0.7

1411.1 1908.49
0.6

2201.09

1500 1800 2100 2400

Wavelength in nm

Measure the wavelength at the minimum of the 2200nm feature in Illite

Albite Zones
Topaz Zone
(high pH)
(low pH)
Airborne SWIR; mineralogy and mica compositions over a porphyry system.
Mineralogy White Mica Composition
High grade,
high sulfidation

Blind Porphyry
Ore grade Cu 200m
below surface

Outcropping
Porphyry Cu

Barren
Advanced argillic
alteration

Illite Wavelength
2195 2215
 Low Temperature Argillic overprints

1
1356.61 2481.16

0.8
2381.85

0.6
2159.97
Norm. HullQ
0.4

1394.31

2207.96
1414.03
0.2
0

1910.01

1500 1800 2100 2400

Wavelength in nm

The feldspars within the porphyry mineralization at Butte have very pervasive
retrograde alteration. This example shows kaolinite replacing feldspar next to a quartz-
moly vein.
Overprinting Signatures; Hypogene and Supergene
s

1
2493
2478

2471

1908

0.9
HullQuot
2484

2451
2343

1411
Sericite

0.8
2199

1400 1600 1800 2000 2200 2400

Wavelength in nm

k Depth

1
0.881

0.823

2498 0.764

2490 0.706
0.9

2447
2379 0.648

0.59

0.532
HullQuot

0.474
0.8

1910
0.416

0.358

0.3
2160
1395
0.242
0.7

1415 0.184

Kaolinite
0.126

0.068
2207

1400 1600 1800 2000 2200 2400 0.01

Wavelength in nm
 White Mica Zonation Model

2210nm
No white mica No white mica 2205nm
2200nm
2195nm

Low temperature argillic

alteration, including illite.
pH buffered by feldspar;
long wavelength illite.
 Spectral Mineralogy Patterns in Porphyry Copper Systems
Short wavelength muscovite in phyllic zones.
Low temperature smectite +/- kaolinite +/- long wavelength illite overprinting HT feldspar
SWIR Mineralogy SWIR Mineralogy
+ Bornite Envelope

White Mica wavelengths Copper grades;

Blue < 2200nm; Red > 2210nm. Blue < 0.1%, Red > 0.6%
 Spectral Mineralogy Patterns in Porphyry Copper Systems
Short wavelength muscovite in phyllic zones.

Sulfide Mineralogy SWIR Mineralogy

SWIR Mineralogy
White Mica wavelengths
Overlaid on Mo soil geochem
Blue < 2200nm; Red > 2210nm.
District-Scale Spectral Mineralogy Patterns in Porphyry-Epithermal Systems
SWIR Mineralogy Illite Wavelength

PCD

LSE

50km LSE

PCD

PCD

LSE

40km
Alteration in Porphyry Cu deposits
Use a K/Al vs Na/Al molar ratio plot to look at alteration trends. Consider a rock that is totally sericitised. The mineralogy of
the rock might be muscovite-quartz-carbonate-pyrite. All of the K and Al in that rock will be within sericite. Muscovite has a
composition of KAl3Si3O10(OH)2. Therefore the ratio of K:Al in the sericitised rock is 1:3. Similarly, a totally KSpar (KAlSi 3O8)
altered rock will have a K:Al ratio of 1:1. In the same way, albitisation can also be tracked. Albite is NaAlSi 3O8: Na:Al =1:1. The
amount of biotite that is formed (potassic alteration) is limited by the amount of Fe available in hornblende. This is what a
K/Al vs Na/Al molar ratio plot looks like from a typical PCD.

Po
ta
ss
ic
alt
er
ati
on

Phyl
lic a
ltera
ti on
g n
Stro

e
erat

Weak
Mod
Copper grades versus Alteration in Porphyry Cu deposits
Porphyry Cu example dominated by phyllic alteration

Illite

Illite-Smectite
Least altered rocks

Smectite
Porphyry Cu example dominated by advanced alteration

Adularia
te)
smecti

Illite
Least-altered rocks
Illite (+

Albite alteration

Advanced Argillic
Porphyry Cu example where the intrusions were emplaced into
reduced country rock.
SO2 + carbon + H2O  H2S + CO2 + H2O; generate reduced S without making acid, therefore little phyllic
alteration.
 Pathfinder chemistry; importance of detection limits
Bismuth assays by ICP-MS, detection limit 0.01ppm Bismuth assays by ICP-AES, detection limit 5ppm
Blind Porphyry Cu deposits Outcropping Porphyry Cu
300m below surface deposit
 Alteration processes and products

Scott Halley
February 15, 2015 Butte, Montana; potassic, phyllic, argillic alteration
 Hydrothermal alteration
mineralogy depends on
properties of the fluid;
• Temperature
• pH
• Salinity
• Oxidation State
• Sulfur Content

Each of these factors also influences

the ability of the fluid to carry metals.

Kapan, Armenia; vuggy quartz-pyrite, AA alteration

 Acidity
• Most hydrothermal reactions involve
acid.

eg, 3KAlSi3O8 + 2H+  KAl3Si3O10(OH)2

+6SiO2 + 2K+

Feldspar + acid = Sericite + quartz +

potassium ions.

Every acid reaction makes the rock more

aluminous (relatively) and removes alkali
cations.

Esperanza, Chile; potassic alteration overprinted by phyllic

 Link between Temperature
and Acidity
HCl  H+ + Cl-

Temperature affects the way acid

behaves. At high temperatures acids
tend to form molecules; at low
temperatures, acids dissociate and
become more active.

Productora, Chile; massive Kspar alteration in dacite with tourmaline matrix in the breccia
 Temperature
A typical hydrothermal system follows a
cooling path from (K)feldspar to
muscovite to illite to interlayered illite-
smectite to montmorillonite (clay).

It is rare to see sericite-rich alteration

above 350o

>350o, black mica (biotite) + feldspar

<350o, sericite + feldspar destruction

In very acid environments, the

mineralogy changes down temperature
from andalusite to pyrophyllite to dickite
to kaolinite
Increasing acid
 Cooling versus heating fluids
• Alkali exchange KAlSi3O8 + Na+ = NaAlSi3O8 + K+

Cooling => potassic

Alteration

Heating => sodic

Alteration

K+/Na+