HYDROTHERMAL ALTERATION: MAIN TYPES AND
IMPLICATIONS ON ORE-FORMING PROCESSES
Roberto Perez Xavier
Departamento de Geologia e Recursos Naturais
Instituto de Geociências – UNICAMP
Campinas (SP) - Brasil
WHY USE HYDROTHERMAL ALTERATION?
Potentially wide dispersion
Easily logged in cores and chips
Techniques available for detection: remote
sensing, PIMA
Reduce risk exploration
Page 1
HYDROTHERMAL FLUIDS IN THE CRUST
Wyborn 2005
from the source to the ore !!
Has this rock been hydrothermally altered ?
Has the texture been preserved?
Granitic rock X1 Au deposit – Alta Floresta Gold Province (Brazil) Rodrigues & Xavier (2010)
Page 2
GE-803
Has this rock been hydrothermally altered ?
Has the texture been preserved?
Granitic rock X1 Au deposit – Alta Floresta Gold Province (Brazil) Rodrigues & Xavier (2010)
GE-803
Has this rock been hydrothermally altered ?
4 cm
João Oficial Au deposit – PAAF - MT). Teixeira & Xavier (2010)
Where is plagioclase? Too much quartz?
Page 3
HYDROTERMAL ALTERATION
Ravenswood Au deposit,
Australia
A common feature in ore
deposits of hydrothermal
origin
halos/envelopes or
alteration zones around
orebodies vectors to
mineral exploration
Extension: millimetre to km’s
(regional scale) Taylor (2009)
tonalite Alteration
zone (dark) -
biotite
HYDROTERMAL ALTERATION
May cause changes of:
colour
texture
mineralogy
chemical
composition
Page 4
Are these all hydrothermal alteration?
alteration
infill
www.antaresminerals.com/Projects/HaquiraPeru
infill alteration
Infill = generally marks the fluid channel breccia, veins, stockworks,
etc
Has this rock been hydrothermally altered ?
X1 Au deposit – Alta Floresta Gold Province (Brazil) Granitic texture still partially preserved
Qtz – pyrite– muscovite – original texture
destroyed
Photo: Rodrigues & Xavier (2010)
What does it reveal about the fluid?
Page 5
Has this rock been hydrothermally altered ?
X1 Au deposit – Alta Floresta Gold Province (Brazil)
Qtz-feldspar porphyry – texture partially Qtz – muscovite – pyrite = original texture
preserved destroyed
Photo: Rodrigues & Xavier (2010)
What does it reveal about the fluid?
HYDROTHERMAL ALTERATION: what does it tell about the
fluid ?
Log aK+/aH+ =
Page 6
HYDROTHERMAL ALTERATION: what does it tell about the
fluid ?
Alkali metassomatism
Hydrolitic (with H+) metassomatism
Log aK+/aH+ =
3KAlSi3O8 + 2H+(aq) ⇔ KAl3Si3O10(OH)2 + 6SiO2 + 2K+(aq)
K-feldspar muscovite/sericite quartz
HYDROTHERMAL ALTERATION: what does it tell about the
fluid ?
Alkali metassomatism
Hydrolitic (with H+) metassomatism
Log aK+/aH+ =
What happens at lower pH conditions at lower or higher
temperatures?
2 KAl3Si3O10(OH)2 + 2 H+ + 3 H2O = 3 Al2Si2O5(OH)4 + 2 K+
muscovite kaolinite
intense leaching of the alkalis = kaolinite stable (pyrophyllite or
andalusite at >350°C)
Page 7
Há indícios de alteração ? Textura da rocha preservada?
Hot Creek Geologic Site (Nevada)
Vulcânica intermediária com alteração
argílica (e.g., caolinita) O que revela sobre o fluido ?
HYDROTHERMAL ALTERATION: what does it tell about the
fluid ?
Alkali metassomatism
paragonite albite
Hydrolitic (with H+) metassomatism
Log aNa+/aH+
1.5 NaAlSi3O8 + H+ = 0.5 NaAl3Si3O10(OH)2 + 3 SiO2 + Na+
albite paragonite
NaAl3Si3O10(OH)2 + H+ + 3 SiO2 = 1.5 Al2Si2O10(OH)2 + Na+
paragonite pyrophylite
Page 8
HYDROTHERMAL ALTERATION
Main controlling factors
Temperature
Pressure
Host rock (composition, grain size, texture,
porosity)
Structures (permeability)
Fluid (composition, P – T – redox conditions)
Fluid/rock ratio
HYDROTHERMAL ALTERATION: fluid/rock ratio
100
F/R mafic rock
titanite hematite ilmenite 0-2 chl + ab + ep + act
80
Composition (vol. %)
2-35 chl + ab + ep + act +
60 chlorite qtz
35-50 chl + ab + qtz
40
> 50 chl + qtz
20 albite
quartz Rock-buffered
0 versus fluid-
0 20 40 60 80 100 120 buffered
seawater/basalt ratios
F/R ratios vary from 0.1 to 4 in hydrothermal systems
F/R ~ 0,1 = all H2O is consumed in the formation of
hydrated silicates
Page 9
HYDROTHERMAL ALTERATION: influence of the host rock
McCuaig & Kerrich (1998)
What is the host rock ?
HYDROTHERMAL ALTERATION: influence of the host rock
What is the host rock ?
Page 10
HYDROTHERMAL ALTERATION: influence of the host rock
What is the host rock ?
TYPES OF HYDROTHERMAL ALTERATION
Mineral Alteration type?
associations
Sericite, quartz, Sericitic, sericitization
pyrite, chlorite
Sericite, chlorite, Phyllic
quartz
Biotite, quartz, Potassic, biotitization
magnetite
Albite, actinolite, Propylitic, Na-Ca
epidote, quartz,
chlorite
Chlorite, epidote, Propylitic
albite, calcite,
actinolite, pyrite
Garnet, Calcic, skarn-type (calc-
clinopyroxene, silicate)
actinolite, epidote
Page 11
TYPES OF HYDROTHERMAL ALTERATION
greisen
Terminologies may reflect:
Formation environment for some deposits: e.g. phyllic
(sericite/muscovite predominant) for PCDs, but sericitic for
VMS
The presence of a dominant mineral: but alteration may
contain more than one dominant mineral
Different minerals but that contain the same dominant
cation (compositional factor)
TYPES OF HYDROTHERMAL ALTERATION
Describing or classifing hydrothermal alteration: what is the
best terminology?
Assemblage = minerals are in contact + coeval descriptive
term
Chlorite – carbonate - epidote
Association = minerals form a group but NOT necessarily in
contact or coeval non-equilibruin conditions
Chlorite, carbonate, epidote
Page 12
TYPES OF HYDROTHERMAL ALTERATION
Describing or classifing hydrothermal alteration: what is the
best terminology?
1. Define assemblages/associations
2. General terminology may then be applicable, but avoid
genetic implications
Use of polished-thin sections may be inevitable sometimes!!
TYPES OF HYDROTHERMAL ALTERATION
Page 13
PROPYLITIC
Epidote + chlorite + albite ± carbonate ± sericite ± pyrite
alteration of plagioclase and Fe-Mg silicates (hornblende,
biotite) selective
Ep
Original texture is preserved =
low fluid-rock ratios
Qtz
Distal parts of mineralized Plg
systems vector to mineral Bt-amp
exploration (clt)
chlorite – epidote alteration in granitic rock (Ravenswood Au
deposit - Austrália – Taylor (2009)
PROPYLITIC
pH
PROPYLITIC – low T
Chl/Sm, Q,
Cb, Zeo
epizonal
Chl, Q,
Cb, Ab
PROPYLITIC – high T
Chl, Q, Ep,
Cb, Ab
temperatura
Sm= smectite
hypozonal mesozonal
Q= quartz
Ep, Act, Cb= carbonate
Chl, Q,Fd, Ab= albite
Cb Act= actinolite
Chl= chlorite
Ep= epidote
Fd= feldspar
Zeo= zeolite
T= > 250°C a < 400°C
low Fluid/Rock ratios
pH = neutral to alkaline
Page 14
POTASSIC ALTERATION
K-feldspar (felsic rocks) and/or biotite (mafic rocks) +
quartz ± magnetite ± hematite
± sulphides (pyrite and chalcopyrite)
Fe3+ =
microscopic
inclusions of
hematite in K-
feldspar
reddish colour
Potassic alteration + hematite in vulcaniclastic unit (Francisco Au-base
metal deposit, Brazil). Assis (2011)
POTASSIC ALTERATION
(PCD – Macquaire Arc – Australia, Mowat & Smith
Page 15
POTASSIC ALTERATION
K-feldspar replacing biotite + magnetite in PCD
weak
bi
bi--mt distal alteration
Moderate
PCD – Cadia, Macquaire Arc –
Australia, Mowat & Smith)
Strong
POTASSIC ALTERATION
pH
POTASSIC
epizonal
Q= quartz
Act= actinolite
FK= K-feldspar
Bt= biotite
temperatura
Cpx= clinopyroxene
hypozonal mesozonal
Mt= magnetite
Tr= tremolite
Gr= garnet
Wo= wollastonite
Act,
Bt, Q,
FK, Gain of K; Ca and Na
cpx, = lost from feldspars
mt
Fe and Mg = lost
Generally indicate high T (> 450°C e < 600°C) from mafic minerals
pH = neutral to alkaline
Page 16
SERICITIC (OR PHYLLIC)
Very common alteration type sericite/muscovitae+ quartzo+ pyrite ±
biotite ± chlorite ± carbonate replacement of feldspars, mica and
Fe-Mg silicates
3KAlSi3O8 + 2H+(aq) ⇔ KAl3Si3O10(OH)2 + 6SiO2 + 2K+(aq)
K-feldspar muscovite/sericite quartz
Francisco Au- base metal deposit, Brazil (Assis, 2011)
If K é added to the system it can develop K-deficient rocks (e.g. mafics)
Deformation/shearing may generate foliation
SERICITIC (OR PHYLLIC)
T= 200 - 250°C e pH= 4 - 6
At highter T it may grade to potassic alteration K-feldspar or biotite
Page 17
ARGILLIC ALTERATION
pH
Si= silica
K K
sil sil, Sm Q= quartz
epizonal
K – ill – Sm
Q - Cb Cb= carbonate
K – Sm - Dp
Q - Cb Dp= Diaspore
temperatura
AlO(OH)
mesozonal
K= kaolinite
Al2Si2O5(OH)4
ill= illite
K0.75(Al1.75Mg0.25)(Si3.5Al0.5)O10(OH)2
hipozonal
Sm= smectite
A0.3(Al1.3Mg0.7)[Si4]O10.(OH)2.xH2O
A= K, Ca, Na
T= < 250°C and pH < 4
Leaching of alkalis and Ca
Strong alteration marked by clay ADVANCED ARGILLIC
mineral associations:
kaolinite ou dickite [Al4Si4O10(OH)8]
+ pyrophyllite [Al2Si4O10(OH)2] ±
quartz ±
alunite [KAl3(OH)6(SO4)2] ± sericite
± andalusite ± diasporo [AlO(OH)] Typical zoning produced by acidic
KAl(SO4)2. 12H2O fluids:
Central zone(dark brown): residual
silica
Intermediate zone (whitish): kaolinite-
alunite;
Outer zone ( light brown): kaolinite-
sericite
Refugio mine, Maricunga Belt, Chile
(Fontboté, 1994)
Page 18
ADVANCED ARGILLIC
pH Si= amorphous
silica
Si Al Q= quartz
Si Al= alunite
And= andalusite
epizonal
Al
K= kaolinite
Al Q
Q K Py= pyrophyllite
Q Di= dickite
temperatura
hypozonal mesozonal
Al
Extreme alkalis and
Q
Ca leaching by
Al Py-Di
acidic fluids (pH < 4)
Q
T > 300°C =
Q And
And pyrophyllite
Q, Py,
Q mica
– andalusite
KAl3Si3O10(OH)2 + 2H+(aq) + 2SO42- ⇔ + KAl3(SO4)2(OH)6 + 3SiO2
K-mica alunite quartz
What happens if Al + alkalis + Ca are all leached
from the rocks?
Silicification = residual silica
Page 19
HYDROTHERMAL ALTERATION: T – pH –
COMPOSITION OF THE FLUID
pH
HYDROTHERMAL ALTERATION IN PORPHYRY Cu-Au-Mo
DEPOSITS
Page 20
HYDROTHERMAL ALTERATION IN EPITHERMAL Au-Ag
DEPOSITS
GREISEN
Similar to sericitic alteration =
quartz (60%) + muscovite
(30%)
.... But with topaz, tourmaline,
and fluorite as accessories
Generally spatially and
genetically associated with
granitic rocks
T = 250 e 450ºC
P = 0.5 e 2.5 kbar Paluma district, Australia; Taylor (2009)
Page 21
SODIC ALTERATION (Na-plag and/or Na-Scapolite)
Pedra Branca IOCG prospect, Carajás (Brazil);
Mizuno (2009)
T > 500°C and highly
Scapolite: saline fluids
Marialite (Na3Al3Si9O24·NaCl) -
hydrothermal Attention !: Albite alteration is
not restricted to high
Meionite (Ca3Al6Si6O24·CaCO3) - temperature systems may also
granulites occur in low T diagenesis
SODIC ALTERATION (Na-plag and/or Na-Scapolite)
Pink albite
presence of
microscopic
inclusions of
hematite Granitoid – Sossego IOCG mine – Carajás, Brazil (Monteiro et al. 2008)
May have regional
extension flow of
high volume of hot and
saline fluids good
for collecting metals
vector to
mineralization
Volcanic - IOCG Ernest Henry - Australia
Page 22
SODIC-CALCIC ALTERATION
Na-Ca
Albite, Ca-
actinolite, epidote,
magnetite
Granitoid – Sossego IOCG mine – Carajás, Brazil
(Monteiro et al. 2008)
Indicate high T:
> 400°C - < 500°C
Olympic Dam IOCG mine – Australia (courtesy
of Roger Skirrow)
CALCIC - FERRIC ALTERATION
IOCG - Mt Elliot (Australia)
Ca-Fe alteration (px - act + mgt) – skarn-type alteration
275 Mt @ 0.6 % Cu and 0.40 g/t Au
Page 23
CALCIC - FERRIC ALTERATION
IOCG - Mt Elliot (Australia)
Mt Elliot (Australia)
calc-silicate - host rock
Page 24
K-Fe alteration (high T)
Can be very difficult to distinguish potassic alteration
from sodic alteration in the field, but K is important to
recognize.
Corriveau, 2010
Options…..
Staining hand
samples (uses
HF and must
be done in the
lab);
Gamma ray
spectrometer-
hand held and
field-ready;
Hand held XRF
http://minerva.union.edu/hollochk/c_petrology/staining_feldspars.htm
http://minerva.union.edu/hollochk/c_petrology/staining_feldspars.htm
A type 4
The unstained hand specimen shows a stage
pyrite–quartz–chlorite–calcite ± hematite
2 quartz–
stringer vein in granodiorite
pyrite–chalcopyrite–alkali feldspar–
is surrounded by quartz, chlorite, and
molybdenite vein and enveloping
hematite. Staining with sodium
pink alkali feldspar alteration in
cobaltinitrite indicates that the pink
granodiorite. Vein and alteration halo
alteration mineral is not alkali
are cut by several stage 6 calcite veins. The
feldspar (right-hand photograph).
matching sodiumcobaltinitrite-
stained hand specimen highlights the alkali
feldspar
selvedge to the vein Duuring et al, Magmatic and structural controls on porphyry-style
Cu–Au–Mo mineralization at Kemess South, Toodoggone
District of British Columbia, Canada. Miner Deposita (2009) 44:435–462,
Page 25
v Close up of a quartz–chlorite–pyrite
±chalcopyrite±sphalerite±gold vein associated with a R fault zone.
Chlorite and pyrite replace alkali feldspar and magnetite alteration in
the granodiorite. vi Staining with sodium cobaltinitrite demonstrates
the replacement of alkali feldspar by chlorite with proximity to the
vein.
Duuring et al, Examining potential genetic links between Jurassic
porphyry Cu–Au±Mo and epithermal Au±Ag
mineralization in the Toodoggone district of North-Central
British Columbia, Canada. Miner Deposita (2009) 44: 463 - 496
AND IF ONE MINERAL IS
BY FAR THE DOMINANT?
Chlorite alteration
(chloritization?),
Carbonate alteration
(carbonatization?, silica
alteration (silicification?)
....
Proximal alteration
- chlorite dominant
Distal alteration - sericitic
Zn-Pb-(Cu-Au) de Aripuanã (MT) Massive sulphides: sphl – gn – py - cpy
Page 26
...AND MORE HYDROTHERMAL ALTERATION !!!
Sulphide alteration
(sulphidation?) in BIF
replacement of siderite by
pyrite around quartz veins
FeCO3 + 2H2S = FeS2 + CO2 +
2H2O
(Xavier et al., 2000)
Cuiabá Au mine - Quadrilátero Ferrífero, Brazil
...AND MORE HYDROTHERMAL ALTERATION !!!
Mt Cobalt U-Co deposit, Australia
Isobella mine (Ag,Pb, Zn), Australia
sph
Taylor (2009)
Taylor (2009)
Silica alteration = silicification + Hematite alteration (reddish zone)
silica infill = hematitization
Page 27
Limestone
Recrystallization, but
restricted changes in the
mineral association (calcite
shows wide P-T stability field)
Marble
Impure limestone
But is it metamorphism
or metassomatism ??
Calc-silicate rock
Carbonate –rich or calc-silicate rocks at pluton contacts Ca –Fe - Mg
silicates (tremolite-actinolite, diopside, Ca garnet, epidote, wollastonite,
phlogopite and biotite
1 cm
1 cm
Frisch and Helgeson (1984); Hal Helgeson. Winter (2001)
But is it metamorphism or metassomatism ?? (in
this case contact metamorphism)
Page 28
Metamorphism or Metassomatism ??
Granulite and
eclogite mineral
assemblages
Granulite indicate similar P-T
conditions
What is the
difference ?
Presence of a fluid
phase =
eclogitization !!
Fluid-induced
PUTNIS AND AUSTRHEIM (2010) reactions
In the absence of fluid the granulite remains essentially unreacted
Metamorphism or Metassomatism ??
METAMORPHISM = reequilibration of mineral
assemblages due to changes in pressure, temperature
and ⁄ or chemical environment texture and mineralogy
change, but NOT the rock composition
METASSOMATISM/HYDROTHERMAL ALTERATION =
reequilibration of mineral assemblages due to changes in
pressure, temperature and ⁄ or chemical environment
texture and mineralogy change AS WELL AS the rock
composition external source for the fluid
Both processes involve material transport but on different
length scales
Every metamorphic reaction is metasomatic on a local scale
Page 29
HYDROTHERMAL ALTERATION : MASS BALANCE
Li et al (2013)
HYDROTHERMAL ALTERATION : MASS BALANCE
Li et al (2013)
Page 30
HYDROTHERMAL ALTERATION : MASS BALANCE
Li et al (2013)
SKARN
High T = > 500°C
Alkaline pH
pH
epizonal
Ca - Skarn =
pyroxene + garnet +
temperatura
wollastonite ±
epidote ± actinolite-
hypozonal mesozonal
tremolite
Mg - Skarn =
forsterite + diopside Tr, Q,
cb
+ talc ± actinolite- cpx,
Q, cb.
tremolite ± calcite gr, wo
Page 31
ALTERATION UNDER METAMORPHIC CONDITIONS
The example of orogenic gold deposits
Greenschist
Greenschist
- amphibolite
Amphibolite
- granulite
McCuaig & Kerrich (1998)
METAMORPHOSED HYDROTHERMAL ALTERATION?
Granulite-facies gneisse with opx Aluminosilicate veins in
and cordierite (Bondy Gneiss amphibolite-facies metamorphosed
Complex, Canada) tuff unit (Musquaro Lake, Canada)
Metamorphism of chlorite Metamorphism of sericitic
alteration ? alteration ?
Bonnet & Corriveau (2007)
Page 32
Alteration zone with andalusite, kyanite, pyrite, chalcopyrite - VMS
deposit (LaRonde Penna, Canada)
Quartz – muscovite – andalusite
schist - footwall of massive
sulphide mineralization (LaRonde
Penna, Canada)
Metamorphism of argillic
alteration ?
http://gsc.nrcan.gc.ca/mindep/synth_dep/gold/vms/i
ndex_e.php
METAMORPHISM OF
HYDROTHERMAL
ALTERATION
ASSEMBLAGES
ARGILLIC ALTERATION
SiO2 – Al2O3 – (FeO/Fe2O3
– MgO – K2O) – H2O
Bonnet & Corriveau (2007)
Page 33
METAMORPHISM OF HYDROTHERMAL ALTERATION
ASSEMBLAGES
SERICITIC
ALTERATION
SiO2 – Al2O3 –
(FeO/Fe2O3 – MgO –
K2O) – H2O
Bonnet & Corriveau (2007)
Qtz – ser - sul bt – KF aluminosilicates – qtz VMS, Au
METAMORPHISM OF HYDROTHERMAL
ALTERATION ASSEMBLAGES
Bonnet, A-L., and Corriveau, L., 2007, Alteration vectors to metamorphosed hydrothermal systems in gneissic terranes, in
Goodfellow, W.D., ed., Mineral Deposits of Canada:ASynthesis of Major Deposit-Types, District Metallogeny, the Evolution
of Geological Provinces, and Exploration Methods: Geological Association of Canada, Mineral Deposits Division, Special
Publication No. 5, p. 1035-1049
Page 34
HYDROTHERMAL ALTERATION IN GNEISSIC TERRANES
Bonnet &
Corriveau
(2007)
REFERENCES
Seedorff E, Dilles JH, Proffett JM, Einaudi MT, Zurcher L, Stavast WJA, Barton MD, Johnson DA (2005) Porphyry-
related deposits: Characteristics and origin of hypogene features. Economic Geology 100th Anniversary Volume,
pp 251-298
Hemley, J.J., and Hunt, J.P., 1992, Hydrothermal ore-forming processes in the light of studies in rock-buffered
systems: II. Some general geologic applications: ECONOMIC GEOLOGY, v. 87, p. 23–43.
McCuaig T.C.; Kerrich R.; Groves D.I.; Archer N. 1993. The nature and dimensions of regional and local gold-
related hydrothermal alteration in tholeiitic metabasalts in the Norseman goldfields: the missing link in a crustal
continuum gold deposits? Mineral. Deposita, 28: 420-435.
Putnis, A.; Austrheim, H., 2010, Fluid-induced processes: metassomatism and metamorphism. Geofluids, 10: 254-
269.
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