Short course for the SEG student

chapter at Universidad Nacional

de Ingenieria, Lima, Peru
Skarn deposits
30 June 2013
Zhaoshan Chang
EGRU, James Cook University, Australia
Zhaoshan.chang@jcu.edu.au
Universidad Nacional de Ingenieria, Lima, Peru
30 June 2013
Skarn deposits
Zhaoshan Chang
EGRU, JCU
Zhaoshan.chang@jcu.edu.au
Skarn deposits
1. Introduction, definition and mineralogy
2. Classification and terminology
3. Skarn-forming processes & evolution stages
4. Zonation in skarn systems
5. Factors affecting the formation of skarns and
zonation patterns
6. Exploration (quiz)
Why skarns?
Au, Cu, Sn, W, Pb, Zn, Mo, Fe, minor Ag, B, Be, Bi, Co, F, REE and
U
Common: >1400 skarn deposits described in literatures
Major source of W and Sn
Significant source of base metals and Au, e.g., Antamina, Peru
(1521 Mt @ 0.9% Cu, 0.5% Zn, 0.02% Mo, 10.9g/t Ag); Ertsberg
district, Indonesia (716 Mt @ 1.2% Cu, 1.2 g/t Au)
High grade sweetener in porphyry deposits
Antamina, Peru. Photo courtesy of Cam McCuaig
Why skarns?
What is a skarn?
Defined by mineralogy: Ca-rich garnet and/or pyroxene
Contact between
intrusions and
carbonate
favorable but not
necessary; not
present at type
locality
Skarn mineralogy
Garnet A
3
2+
B
2
3+
C
3
4+
O
12

Pyroxene A
1
2+
B
1
2+
C
2
4+
O
6

Olivine A
1
2+
B
1
4+
O
4

Pyroxenoid A
1
2+
B
1
4+
O
3

Epidote A
2
2+
B
3
3+
C
3
4+
O
12
(OH)
2

Amphibole A
1
1+
B
2
2+
C
5
2+
D
8
4+
O
22
(OH)
2

Mica A
1
B
2-3
C
4
O
10
(OH, F)
2

Carbonate A
1
2+
CO
3

Others
Spessartine Mn
3
Al
2
(SiO
4
)
3
Almandine Fe
3
Al
2
(SiO
4
)
3
Pyrope Mg
3
Al
2
(SiO
4
)
3

Subcalcic
garnet
Skarn mineralogy
Garnet A
3
2+
B
2
3+
C
3
4+
O
12

Grossular Ca
3
Al
2
(SiO
4
)
3
Andradite Ca
3
Fe
2
(SiO
4
)
3

Grandite
Pyroxene A
1
2+
B
1
2+
C
2
4+
O
6
Diopside CaMgSi
2
O
6
Hedenbergite CaFe Si
2
O
6
Johannsenite CaMnSi
2
O
6

Salite
Garnet and pyroxene composition diagrams
Inappropriate pyroxene composition diagram
Skarn mineralogy
Pyroxenoid A
1
2+
B
1
4+
O
3


Ferrosilite FeSiO
3

Rhodonite MnSiO
3

Wollastonite CaSiO
3
Pyromangite
Bustmite
Epidote A
2
2+
B
3
3+
C
3
4+
O
12
(OH)
2


Epidote Ca
2
FeAl
2
Si
3
O
12
(OH)

Clinozoisite Ca
2
AlAl
2
Si
3
O
12
(OH)

Classification of skarns
Major economic metal:

- Fe, Cu, Pb-Zn, Au, W, Sn, Mo
Magnetite is abundant in many types:

- Cu, Au, Sn
Pb-Zn skarns mostly polymetallic (e.g., with Ag)

Classification of skarns
Endoskarn vs. exoskarn:
Exoskarn is typically much more abundant than endoskarn:
Endoskarn
at Mt Colin
Classification of skarns
Ca-skarn: protolith = limestone
- Garnet, pyroxene, wollastonite, scapolite, Ca-rich plagioclase,
vesuvianite, epidote, amphibole, ilvaite, chlorite, prehnite, biotite,
quartz, carbonate


Mg-skarn: protolith = dolomitic
- Olivine, pyroxene, humite, clinohumite, periclase, amphibole,
phlogopite, chlorite, serpentine, talc, burcite


Mn-skarn:
- Johannsenite, spessartine, rhodonite, pyromangite, bustmite

Distal locations; Pb-Zn skarn;
a subgroup of Ca-skarn
Magmas contain volatiles
(H
2
O, HCl, SO
2
, CO
2
, HF,
B, ) and metals
White Island, New Zealand:
~300 t Au & ~1 Mt Cu discharged to
atmosphere in the past ~10,000 yrs
Courtesy of Jeff Hedenquist
Skarn-forming processes
Water solubility and exsolution
Burnham (1979, 1981, 1997)
Water in aqueous
phase - Magmatic
Hydrothermal fluid
Water dissolved
in melt
Solubility curve
Water solubility and exsolution
Burnham (1979, 1981, 1997)
Water dissolved
in melt
Water in aqueous
phase - Magmatic
Hydrothermal fluid
Second
boiling
First boiling
Rapid ascent;
adiabatic
depressurisation
Cooling /crystallisation
in a chamber
Slow ascending
accompanied by
cooling
Burnham (1979, 1981, 1997)
Second boiling
First boiling
Rapid ascending;
adiabatic depres-
surisation
Cooling /crystallisation in a
chamber
Slow ascending
accompanied by
cooling
Water solubility and exsolution
Water dissolved
in melt
Water in aqueous
phase - Magmatic
Hydrothermal fluids
Water exsolution
Burnham (1979, 1981, 1997)
1. Water slowly exsolves;
P increases; water not
released from chamber
yet due to solid carapace
Quartz USTs, North
Parkes, NSW
Buoyant hydrothermal fluid migrates upwards through the melt
and accumulates in the roof of the inwardly-crystallizing magma
Bands of distinctly prismatic crystals (e.g., qz, mt) grow
downwards from the roof of the volatile pocket
Volatile accumulation
and UST growth
UST quartz form here.
Coalesced water
bubbles. If caught in
melt, miarolitic cavities
will form.
Slide from Dave Cooke
Miarolitic cavities
Candela and Blevin (1995); Candela (1997)
Coarser grained domain; crystals terminated in or project into void
Pockets of magmatic hydrothermal fluids; inward growth
Maybe interconnected ! water migration channel in magma
Field of view = 10cm
Field of view = 2.5 cm
Cavity
UST
quartz
Lowenstern and Sinclair (1996)
Water exsolution
Burnham (1979, 1981, 1997)
2. Internal P > (lithostatic P + carapace
tensile strength, ~100 bar), ! Hydro-
fracturing; P drops by ~75%. Form
magmatic hydrothermal breccia and
quartz veins/networks.
Burnham (1979, 1981, 1997)
3. Pressure drop causes decrease
of water solubility ! rapid
degassing; Water takes away a lot
heat, causing quenching (pressure
quenching); Form porphyry texture
Water
exsolution
Water exsolution
Burnham (1979, 1981, 1997)
4. Seal; Magma at
depth continues to
crystallise; another
cycle
4. Seal; Magma at
depth continues to
crystallise; another
cycle
Water exsolution
Burnham (1979,
1981, 1997)
5. Water exsolves from
deep seated magma
through second boiling
5. Wall rock is ductile at
depth; no explosion, only
expansion; pegmatite
Transitional stage physical
processes
Burnham (1997)
F
W
S
: H
2
O solubility as mass
fractionation
P
t
V
t
: max. mechanical energy
released upon complete crystallisation
MTS: max. tensile strength of rock,
equiv. 100 bar
For Bingham quartz
monzonite with 2.7 wt
% initial water,
hydrofracturing occurs
at depth < ~ 4-5km
Transitional stage chemical processes
Burnham (1981, 1997)
Crystal + melt + aqueous fluid
" Aqueous fluid extracts metals and volatiles from melt
" Interaction between water and crystals (e.g., Chang and
Meinert, 2004)
" Crystallisation continues from melt
Transitional stage chemical processes
Burnham (1981, 1997)
Elemental partitioning between aqueous phase and
melt
" Cl: coefficient = 40:1; Cl in melt: ~0.03 of H
2
O wt% in melt
! NaCl wt% in aqueous fluid = 2 x H
2
O wt% in melt
! if 3-6 wt% H
2
O in melt, then ~6-12 wt% NaCl in
aqueous fluid
" S (SO
2
vs. H
2
S; redox state), CO
2


" F: 5:1
" Most metals prefers aqueous phase, e.g., Cu: 9:1 (Candella
and Holland, 1984)
Timing of water exsolution
Burnham (1981, 1997)
Proportion of melt crystallised at water exsolution

Starting conditions: Dioritic to granitic melt, 2 wt% H
2
O,
Pressure

Depth H
2
O solubility % of crystalli. at water saturation

5000 bars 20 km 10-11 wt% 80%
2000 bars 8 km 6.3 wt% 68%
500 bars 2 km 3.0 wt% 33%
Water exsolution may occur at much higher
temperatures than magma solidus temperatures

Burnham (1981, 1997)
Timing of exsolution affects metal concentration in
aqueous fluids
" Some elements can be taken into igneous minerals, e.g.,
Fe, and some Cu ! early exsolution favourable

" Some trace elements may only become enriched enough
at the end of crystallisation (high degree of crystalli.), e.g.,
Be ! late exsolution favourable

L+V
V
L
Single phase
H+V
H+L
L+H+V
80% 20%
Evolution of magmatic fluids
Magmatic
fluid
At shallow depths (< 4 km)
aqueous magmatic fluids
split into two separate phases
GAS PHASE
low density
high SO
2
, HCl
low NaCl, metals

LIQUID PHASE
higher density
low SO
2
, HCl
high NaCl, metals

Partitioning changes
with changes in P, T

Magmatic vapor

Water solubility and exsolution
Burnham (1979, 1981, 1997)
Water dissolved in
melt
Water in aqueous
phase - Magmatic
Hydrothermal fluid
Carbonate-rich area:
magma assimilates
carbonate ! CO
2

increases ! H
2
O
solubility decreases
! exsolution occurs
earlier (Meinert, 1995)
Hypogene, up to 850 C
vapors, with HCl, SO
2
,
CO
2
, H
2
S
White Island, New Zealand; Courtesy of Jeff Hedenquist
High temperature degassing
" Such magmatic hydrothermal fluids rich in Si and Fe
" Al typically has low solubility, except when acidity is
high or F content is high
Sn-associated Mole granite; Audetat et al., 2000
Fe up to 21.6 wt%
Empire Cu-Zn skarn;
Chang and Meinert, 2004
Skarn-forming processes
Evolution of
skarns - 1
Thermal metamorphism:
- Isochemical
Meinert, 1992
Before magmatic water
is released out from
magma chamber; no
fluid flow
Meinert, 1992
Metamorphism:
Thermal metamorphism
Calcareous: containing carbonate
Carbonaceous: containing organic C
Bimetasomatism:
Calc-silicate
hornfels
Biotite
hornfels
Pyroxene
hornfels
Biotite
hornfels
" Very fine grained
" Low permeability;
block fluid flow;
none to weakly
mineralized
" Garnet rich in Al
Meinert, 1992
Metamorphism:
Thermal metamorphism
Bimetasomatism:
Reaction skarn
Zoned; fine-grained; low permeability; garnet Al-rich; miner. poor
Marble
Garnet
Pyroxene
Garnet
Marble
Reaction skarn
Zoned; fine-grained; low permeability; garnet Al-rich; miner. poor
Reaction skarn
Evolution of
skarns - 1b
Skarnoid
- Fine-grained,
- High Al, low Fe
Meinert, 1992
Small scale fluid
flow along fractures,
promoting minor
mass exchange
Skarnoid at small
scale
Reaction skarn and skarnoid

Metasomatic skarn,
prograde
- Garnet, pyroxene,
wollastonite,
- Olivine, pyroxene,
periclase,
Meinert, 1992
- Large scale fluid flow
- Massive; protolith texture
obliterated
- Higher Fe in skarn minerals
- Zoned
- May over print calc-silicate
hornfels, reaction skarns
Evolution of
skarns - 2
- Protolith texture mostly obliterated
- Ground preparation
Massive garnet skarn
0.5 cm
Calcite to garnet:
CO
2
lost; density increased; mineral tends to be granular !
mineral volume decreased, open space created,
permeability and porosity increased
Mt Colin
Massive
pyroxene
skarn
Elaine
Replacement of hornfels
Evolution of
skarns - 3
Retrograde skarn and
mineralisation

- ep, act/tr, qtz, + mt/hm
- chl, qtz, cal, + sulfides
- cal
Mostly in skarn but may go
beyond
Meinert, 1992
ep: epidote; act: actinolite; tr: tremolite; cal: calcite; qtz:
quartz; chl: chlorite; mt: magnetite; hm: hematite
" Metals dissolved as complexes (e.g., with Cl);
" High solubility at higher temperatures;
" Not deposited until lower temperatures or losing the ligands
(e.g., by dilution)
" Deposition when solubility decreases dramatically
Magnetite
Chalcopyrite
Sphalerite
Galena
500-400C ? 400-250C
?
300-200C ?
Williams-Jones et al. (2010) pH
Base metals in hydrothermal fluids
- Transported as Cl complexes (e.g., Wood and Samson, 1998)
- Deposition causes acidity increase
ZnCl
4
2-
+ H
2
S = ZnS + 4Cl
-
+ 2H
+
Concentrated vs.
dispersed: wall rock
important
Carbonate-rich region
good for base metal
deposition ! higher grade
Retrograde alteration and mineralization
Garnet
Epidote Quartz
Epidote replaces and pseudomorphs garnet
Retrograde alteration
and mineralization
Pyroxene replaced by ilvaite, quartz, and siderite
Reflected + transmitted light
Ilvaite replaced by siderite+quartz
llvaite
llvaite
Calcite
Reflected light
Siderite+
minor quartz
llvaite
Siderite+
minor quartz
Original ilvaite
boundary
Transmitted light, plane polarized
Pyroxene replaced
by quartz, siderite,
and sphalerite
Magnetite is later than prograde skarn;
Sulfides later than oxides

Retrograde alteration and
mineralization
Garnet
Chl + mt
Qtz-cal-py-cpy
Garnet
((
Garnet

Garnet
Mt + chl
Py + cpy Py + cpy
Retrograde alteration and mineralization
Note thin chlorite between sulfides and garnet
Black chlorite selectively replaces bands of
garnet. Note sulfides are associated with
chlorite-quartz-carbonate.
Ga: garnet; Cc: calcite; Qz: quartz; Chl: chlorite; Cpy: chalcopyrite;
Py: pyrite; Bn: bornite
Quartz-calcite-sulfides replace some
bands of garnet and fill the interstices
Cpy Cpy
Cpy
Cpy+Chl Cpy+Chl
Qz+Cc
Retrograde alteration and
mineralization
Chang and Meinert, 2008
Retrograde alteration and
mineralization may be
present beyond skarn
Chl
Po
Cpy+Py
+Au
Retrograde alteration & mineralization
Chl: chlorite; Cpy: chalcopyrite; Py: pyrite; Po: pyrrhotite
Cpy
Granite
porphyry
Hornfels
Skarns are typically zoned
Transfer of heat and mass from intrusions or fluid conduits
Intrusion Calcareous wall rock
Endoskarn Massive/metasomatic skarn
B
l
e
a
c
h
e
d

m
a
r
b
l
e

Marble Limestone
Hornfels
Fluid escape structures
Garnet/pyroxene ratio decrease
Garnet colour lighter
Pyroxene colour darker
Cu
Zn-Pb
Exoskarn is typically much more abundant than endoskarn
Reaction skarn
The closest intrusion is not necessarily the causative intrusion!
Zonation in a Cu skarn
gar: garnet; pyx: pyroxene; cp: chalcopyrite; wo: wollastonite;
ves: vesuvianite; bn: bornite; po: pyrrhotite; py: pyrite
Carr Fork, Bingham, USA
Atkinson and
Einaudi, 1978
38.3m Endoskarn.
Dark red garnet 45.2m Red garnet 46.3m Brown garnet 48.2m Yellow garnet
54.2m Light yellow
garnet
Zoning away from intrusion in a Cu skarn
Zonation in a Cu skarn
Carr Fork, Bingham, Cu skarn
Zonation in a Zn skarn
Marble
Groundhog,
USA;
Meinert,
1987
Gar: garnet; Pyx: pyroxene; Hd: hedenbergite; Jo: Johannsenite
Zonation in a Au skarn Fortitude, USA
Meyer and Meinert, 1991
Zonation at marble front in a Au skarn, Mexico
Dark
marble
Bleached marble Wollastonite Garnet
Fluid escape structures distal
features beyond skarn
Meinert et al., 2005
Pyroxene
Garnet
V
e
i
n
s

[

V
e
i
n
s
Garnet
Garnet veins Garnet veins
Meinert et al., 2005
50-100m away from skarn
Meinert et al., 2005
200m away from skarn
Stylolite
Calcite vein offset by stylolite fluid escape structure
Meinert et al., 2005 Meinert et al., 2005
Fluid escape structures distal
features beyond skarn
Fluid escape structures distal features beyond skarn
Beyond bleached marble, there are white, bleached
veins with diffusive sulfide veins in the middle. The vein
density and width decrease away from skarn
Dark marble
Diffusive veins
(po-cpyMo) Bleached
halo
Fluid escape structures distal features beyond skarn Fluid escape structures distal features beyond skarn
Diffusive veins
(po-cpyMo)
Factors affecting the formation of skarns
Redox state gradient between magma and wall rock

Causative magma
Volatiles
Degree of fractionation
Redox state
Wall rock
Composition
Redox state
Permeability
Depth of formation
Distance from magma
Grossular Ca
3
Al
2
(SiO
4
)
3
Andradite Ca
3
Fe
2
(SiO
4
)
3

Diopside CaMgSi
2
O
6
Hedenbergite CaFeSi
2
O
6
Redox state gradient
Oxidizing Reducing
Fe
3+
! garnet Fe
2+
! pyroxene
Intrusion Calcareous wall rock
Endoskarn Massive/metasomatic skarn
B
l
e
a
c
h
e
d

m
a
r
b
l
e

Marble Limestone
Hornfels
Fluid escape structures
Garnet/pyroxene ratio decrease
Garnet colour lighter
Pyroxene colour darker
The zoning pattern is based on:
If both the magma and the wall rocks are reducing
Ettlinger, 1990; Ray et al., 1996
Ilmenite-
bearing
Fe
2
O
3
/(Fe
2
O
3
+FeO)
= 0.15
Nickle Plate ,
Hedley District,
Canada
If both the magma and the wall rocks are oxidizing
A Cu skarn prospect, Philippines
High in
magnetite
Diorite
Porphyry
Conglomerate
marble
38.3m Endoskarn.
Dark red garnet 45.2m Red garnet 46.3m Brown garnet 48.2m Yellow garnet
54.2m Light yellow
garnet
Specularite
If both the magma and the wall rocks are oxidizing
Effect of magmatic volatiles - F
Empire Cu-Zn skarn, USA
Chang and Meinert, 2004, 2008
Unusual features: 1) Abundant endoskarn, > exoskarn
2) Proximal Zn minearlisation
Effect of magmatic volatiles - F
High F content in the magmatic-hydrothermal system as indicated by:
Empire Cu-Zn skarn mine, USA
Chang and Meinert, 2004, 2008
1.53-2.46 wt% F in magmatic
hornblende
1.43-3.87 wt% F in magmatic biotite
Fluorite as igneous accessory mineral
Fluorite as daughter mineral in fluid
inclusions
1.29-2.42 wt% F in hydrothermal
vesuvianite
Fluorite in skarns
Effect of magmatic volatiles - F
Reasons for these unusual features:
- F greatly facilitates the dissolution of silicates
- F decreases the solidus temperatures of
magmas. When the late-stage fluids exsolved
from them, the fluids were already at low
temperatures, therefore only short
transportation distance was needed for the
fluids to be cool enough to deposit sphalerite
Empire Cu-Zn skarn mine, USA
Chang and Meinert, 2004, 2008
Textures indicating high F
Chang and Meinert, 2004, 2008
Effect of causative magma compositions
Intrusions associated with
Fe and Au skarns: more
primitive

Associated with Mo and Sn
skarns: more evolved and/or
crustally contaminated


Mostly calc-alkaline;
tholeiitic and alkaline not
common
Meinert, 1995
Meinert, 1995
Intrusions associated with Sn skarns: peraluminous
Sn and Au-only skarns: more reduced causative intrusions
Cu, Zn, and Mo skarns: more oxidized causative intrusions
Meinert, 1995
Effect of causative magma compositions
Sn skarns
Intrusive rocks peraluminous, more evolved and/or with more
crustal contamination, and more reduced

Suite of trace elements: Sn, F, B, Be, Li, W, Mo, and Rb

Strong greisen alteration

Sn can be incorporated into silicate minerals, e.g., garnet (up to 6
wt%), vesuvianite, and titanite; extensive retrograde or greisen
alteration needed to release such Sn; most attractive ore bodies
distal

Economic Sn in cassiterite, stannite, vonsenite (4FeOFe
2
O
3
B
2
O
3
),
etc.

Plane-polarized
Pyroxene
Vonsenite
Plane-polarized
Hornblende
Garnet
Calcite
A Sn skarn in western Tasmania, Australia
Garnet
Calcite
Hornblende
Vonsenite Vonsenite
Residual Hb
Fe-rich hb with
bio replacement
Bio with
residual hb
Cassiterite
in this band
Biotite
Cassiterite Cassiterite
Biotite
Fluorite
Pyrrhotite
A Sn skarn in western Tasmania, Australia
Redox
W
W
W
Composition Ca skarn vs. Mg skarn
Porosity, composition
CaCO
3
+ SiO
2(aq)
= CaSiO
3
+ CO
2


W: wollastonite, P: pyroxene, G: garnet
C + O
2
= CO
2
Effect of wall rocks
Geometry
- Massive/irregular vs. stratiform
Effect of wall rocks
Geometry {{]){

Massive/irregular vs.
stratiform
Effect of wall rocks
Chang et al., 2007
Stratiform skarn
Chang et al., 2007
Effect of wall rocks
Meinert, 1992
Depth of formation
- Ambient temperature
- Metamorphism
- Retrograde alteration

- Permeability
W skarn vs. Cu skarn

W skarn
Musc - hm - chl - qtz
Musc - hm - chl - qtz
Bio - sill - alm - ilm
cord ksp qtz
Granodiorite
Bio - sill - ilm cord
Bio - adl - sill - ilm
W skarn
W skarn
Granodiorite
porphyry
Skarn
Cu skarn
Distance from causative intrusion
Fluid temperatures
Distal skarns
are rich in Mn
Johannsenite,
rhodonite,
pyromangite,
bustmite
Meinert, 1992
Zonation in skarns - summary
Quiz
A granodiorite intrusion contains ilmenite but no magnetite
Fe
2
O
3
/(Fe
2
O
3
+FeO) < 0.2
The wall rocks ~800m away
from the intrusion are dark in
colour
Sandstone
Shale
Limestone
Quiz
If there are skarns between such an intrusion and
wall rocks, how wide would the skarn zone likely
be?


1) A few meters
2) Tens of meters
3) Hundreds of meters
Quiz
In the zoning pattern, which zone would be the
major one?


1) Garnet > pyroxene zone
2) Garnet pyroxene zone
3) Garnet < pyroxene zone
Quiz
Around the intrusion some biotite hornfels containing
disseminated pyrrhotite were found. What kind of
economic metal(s) may the skarn contain?

1) Fe 2) Cu 3) Au
4) Pb-Zn 5) W 6) Sn
Biotite
hornfels
Pyroxene
hornfels
Quiz
In the intrusion there are some garnet veins with green
pyroxene halo close to contact, but there is no greisen
alteration. With this additional information, please estimate
again what economic metal(s) the skarn may contain:

1) Fe 2) Cu 3) Au
4) Pb-Zn 5) W 6) Sn

Quiz
Estimate the composition of the garnet. Is it

1) Rich in Al (grossularitic), or
2) Rich in Fe (andraditic), or
3) Rich in Mn (spessartine)
Quiz
Narrow garnet
margins; majority
grossularitic
Garnet composition
1
2
3
4
Where would
you drill?
Why?

Quiz
1
3 4
Quiz
Is the granite
porphyry the
causative
intrusion for
the skarns?
Why or why
not?

Quiz