Hydrothermal

altera-on –
Some key points
Lluís Fontboté
Dept. Earth Sciences, Univ. Geneva, Switzerland

Honorary Lecturer Society of Economic Geologists (SEG)

MINERAL RESOURCES AND GEOFLUIDS

Earth and Environmental Sciences

Main messages:
■ Altera-on gives informa-on on mineralizing
fluids: pH, T, redox state….
■ Look at cross-cuKng rela-onships and
zoning!
■ Remember: altera-on gives informa-on on
the fluid chemistry directly in the field!

L. Fontboté, July 26, 2018, p. 1

 Refugio, Maricunga, Chile

© L. Fontboté (2003)

Typical zonaDon formed by acidic fluids


ser kaol-ser
kaol-alun

residual silica
kaol-alun

Refugio HS Au Deposit, Maricunga

Belt, northern Chile.
(Photo LF 1994.10-4/06)

L. Fontboté, July 26, 2018, p. 2

 Typical zonaDon formed by acidic fluids


--- ph 4

ser kaol-ser
kaol-alun

residual silica
kaol-alun

--- ph 1

Refugio HS Au Deposit, Maricunga

Belt, northern Chile.
(Photo LF 1994.10-4/06)

Hdrothermal altera-on – The search

of a new equilibrium
■  Hydrothermal alteraDon can be defined as the conversion of an original
mineral associaDon in a new mineral associaDon that is more stable under
the new condiDons of temperature, pressure and composiDon of a
hydrothermal fluid migraDng through the rock
■  The original structures and textures can be slightly or completely changed by
hydrothermal alteraDon

Orebody

Alteration I

Alteration II

L. Fontboté, July 26, 2018, p. 3

 Hydrothermal alteraDon, which, for the study of primary mineral assemblages
is a nuisance, can be very helpful:

(I) exploraDon guide (ore deposits and geothermy)

(Ii) aid to determine the chemical nature of hydrothermal soluDons and their
sources, and
(Iii) to understand the evoluDon of the hydrothermal system.

The study of acDve hydrothermal systems (e.g. well studied in New Zealand,
Iceland, Yellowstone ...) is an important source of informaDon.

Orebody

Alteration I

Alteration II

Hydrolysis and hydrogen ion metasoma-sm

•  An important concept: hydrolysis* reac-on (not hydra'on**!)
•  The stability of feldspar, mica and clay minerals at 300° C is to a large extent controlled by
the following hydrolysis reac-ons:
1.5KAlSi3O8 + H+ ⇔ 0.5 KAl3Si3O10(OH)2 + 3 SiO2 + K+ (1)

K-fspr muscovite quartz
KAl3Si3O10(OH)2 + H+ + 3/2 H2O ⇔ 3/2 Al2Si2O5(OH)4 + K+ (2)

muscovite kaolinite
- The hydrolysis reactions above are ion-hydrogen metasomatism reactions, and,
thus, favored by acidity.
=> Zoning rocks in equilibrium with more acidic and less acidic fluids!

Equivalent reacDons also by alteraDon of Na minerals

0.75Na2CaAl4Si8O24 + 2H+ + K+ = KAl3Si3O10(OH)2 + 1.5Na+ + 0.75Ca2+ + 3SiO2


andesine muscovite
1.5NaAlSi3O8 + H+ = 0.5NaAl3Si3O10(OH)2 + 3SiO2 + Na+

albite paragonite
NaAl3Si3O10(OH)2 + H+ + 3SiO2 = 1.5Al2Si4O10(OH)2 + Na+

paragonite quartz kaolinite

*) The phenomenon by which K+, Na+, Ca2 +, Mg2 + and other cations are transferred from the mineral into the solution and H+
into the solid phase.
**) Example of hydration : 2Mg2SiO4 + H2O + 2H+ = Mg3Si2O5(OH)4 + Mg2+
olivine serpentine

L. Fontboté, July 26, 2018, p. 4

 Hydrolysis and hydrogen ion metasoma-sm
•  An important concept: hydrolysis* reac-on (not hydra'on**!)
•  The stability of feldspar, mica and clay minerals at 300° C is to a large extent
controlled by the following hydrolysis reac-ons:
1.5KAlSi3O8 + H+ ⇔ 0.5 KAl3Si3O10(OH)2 + 3 SiO2 + K+ (1)

K-fspr muscovite quartz
KAl3Si3O10(OH)2 + H+ + 3/2 H2O ⇔ 3/2 Al2Si2O5(OH)4 + K+ (2)

muscovite kaolinite

- The hydrolysis reactions above are ion-hydrogen metasomatism reactions,

and, thus, favored by acidity.
=> Zoning rocks in equilibrium with more acidic and less acidic fluids!

*) The phenomenon by which K+, Na+, Ca2 +, Mg2 + and other cations are transferred from the mineral into the
solution and H+ into the solid phase.
**) Example hydration : 2Mg2SiO4 + H2O + 2H+ = Mg3Si2O5(OH)4 + Mg2+
olivine serpentine

Base Exchange

■  ReacDons where there is an exchange of caDons between the soluDon and a

mineral are called caDon exchange basis ("base exchange"). A typical example is a
microcline albiDzaDon or the contrary process.

KAlSi3O8 + Na+ = NaAlSi3O8 + K+

K-feldspar albite

L. Fontboté, July 26, 2018, p. 5

 Hydrogen ion metasoma-sm
a) System K2O-Al2O3-SiO2-H2O (and chlorinity)

3KAlSi3O8 + 2H+ = KAl3Si3O10(OH)2 + 2K+ + 6SiO2


K-fsp muscovite quartz

KAl3Si3O10(OH)2 + H+ + 3/2 H2O ⇔ 3/2 Al2Si2O5(OH)4 + K+ (2)


muscovite kaolinite

upper curves: pH of fluid in equilibrium with the buffering assemblage K-feldspar-

muscovite-quartz

lower curves: pH of fluid in equilibrium with the buffering assemblage kaolinite-

muscovite-quartz) as a func-on of fluid chlorinity
(Yardley and Bodnar, 2014)
T: 275°C (solid lines) and 252 °C (broken curves, )
P: on the boiling curve of water.

b) System Na2O-Al2O3-SiO2-H2O

1.5NaAlSi3O8 + H+ = 0.5NaAl3Si3O10(OH)2 + 3SiO2 + Na+


albite paragonite

NaAl3Si3O10(OH)2 + H+ + 3SiO2 = 1.5Al2Si4O10(OH)2 + Na+


paragonite quartz pyrophyllite

1.7NaAlSi3O8 + H+ = 0.5Na.33Al2.33Si3.67O10(OH)2 + 1.67SiO2 + Na+


albite Na-montmorillonite

3Na.33Al2.33Si3.67O10(OH)2 + H+ + 3.5H2O = 3.5Al2Si2O5(OH)4 + 4SiO2 + Na+


Na-montmorillonite kaolinite

3NaAlSi3O8 + 2H+ + K+ = KAl3Si3O10(OH)2 + 6SiO2 + 3Na+


albite muscovite

■  The reactions move to the right if pH decreases!

L. Fontboté, July 26, 2018, p. 6

 Evolution of a cooling fluid. 1 kb. Quartz present

K-Feldspar KAlSi3O8

Musc., Ser. KAl3Si3O10(OH)2

Kaolinite Al2Si2O5(OH)4
Pyrophyllite Al2Si4O10(OH)2

Albite NaAlSi3O8

Paragonite NaAl3Si3O10(OH)2


musc + H+
kaol + K+

At 400°C and 1kb. Quartz present

(After Meyer and Hemley 1967)

(pH = negative logarithm of H+ concentration)

SO4= bearing systems

alunite forma-on
KAl3Si3O10(OH)2 + 4H+ + 2SO42- = KAl3(SO4)2(OH)6 + 3SiO2

muscovite alunite

3Al2Si2O5(OH)4 + 2K+ + 6H+ + 4SO42- = 2KAl3(SO4)2(OH)6 + 6SiO2 + 3H2O


kaolinite alunite

Stability relations of alunite, kaolinite, muscovite and

K-feldspar as a function of the activities of K2SO4 and
H2SO4 (After Hemley et al. 1969)

L. Fontboté, July 26, 2018, p. 7

 Albite NaAlSi3O8
Montmorrillonite
(Na,Ca)0,3(Al,Mg)2Si4O10(OH)2·n(H2O)
Paragonite NaAl3Si3O10(OH)2
Kaolinite Al2Si2O5(OH)4
Alunite KAl3(SO4)2(OH)6

Diagramatic representation of hydrothermal alteration in rocks containing

A dominant alkali-feldspar and B dominant calcic plagioclase (after Hemley and
Jones, 1964 in Pirajno, 1992)

The "Hemley diagram"

Seedorf, 2008

L. Fontboté, July 26, 2018, p. 8

 Altera-on example: The porphyry system

Kouzmanov and Pokrovski, 2012

Main altera-on types-1

(according increasing acidity)
■  Potassic alteration (alkaline metasomatism)

•  High T: 800 to 600°C

•  Residual fluid derived from an intrusion: minerals that precipitate (K-Fd,
biotite, ± magnetite…) similar to those of intrusion.
•  Close to neutrality
•  Neutral

L. Fontboté, July 26, 2018, p. 9

 Potassic alteration:
Intimately associated with initial
stockwork veining at T>400°C

Cation exchange between cooling magmatic

fluid and wall rocks

NaAlSi3O8 + K+ = KAlSi3O8 + Na+

rock fluid rock fluid

Magmatic &
hydrothermal biotite
-  Magmatic (“book”) biotite
-  Hydrothermal (“shreddy”) biotite:
disordered appareance, alteration
product on another mineral,
commonly amphibole or another
ferromagnesian mineral

L. Fontboté, July 26, 2018, p. 10

A-B qtz veinlets, "shreddy" bio-te, magma-c "book" bio-te,

El Salvador, Chile

© L. Fontboté (2003)

A-B qtz veinlets, shreddy bio-te, El Salvador, Chile

© L. Fontboté (2003)

L. Fontboté, July 26, 2018, p. 11

 Altered Intrusive Rocks – Potassic
Altera-on
pyroxene relict

shreddy bio-te Tourmaline >400C

Bio-te >325 C

Main altera-on types-2

(according increasing acidity)
■  Sericitic

•  Intermediate to low T: 600° - 250 °C

•  Acid
•  qz-ser-py most typical assemblage
(Destabilization of feldspaths in presence of H+, S, K, OH)

L. Fontboté, July 26, 2018, p. 12

 Veinlets in porpyhry systems
(according to Einaudi, 1996; based son the work by Gustafson and Hunt (1975) on El Salvador, Chile)

Quartz-sericite veins (D-veins), El Salvador, Chile

L. Fontboté, July 26, 2018, p. 13

Quartz-sericite veins (D-veins), Yerington, Nevada, USA

Main altera-on types-2

(according increasing acidity)
■  Argillic

•  Intermediate to low T: 600° - 250 °C

•  Acid
•  qz-ser-py most typical assemblage
(Destabilization of feldspaths in presence of H+, S, K, OH)

L. Fontboté, July 26, 2018, p. 14

 Altera-on example: The porphyry system

Kouzmanov and Pokrovski, 2012

Main altera-on types-3

(according increasing acidity)
■  Advanced argillic (AA)

•  600° - 200 °C
•  Intense H+ metasomatism ( very acid!). Destabilization of silicates.
•  kaolinite (3Al2Si2O5(OH)4, dickite (Al2Si2O5(OH)4), other clays

•  If more acid: aluminum liberated by silicates fixed in alunite

KAl3(SO4)2(OH)6 and diaspore AlO(OH).

•  If still more acid, even Al and all other elements except Si and Ti are totaslly
leached: residual quartz ("vuggy silica")

L. Fontboté, July 26, 2018, p. 15

 © L. Fontboté (2003)

Residual ("vuggy") silica

© L. Fontboté (2003)

L. Fontboté, July 26, 2018, p. 16

Typical vuggy (or residual) silica in the central part of the 

Marcapunta Au-Ag prospect, Colquijirca District, Central Peru.
(Photo 1998.3/11)

L. Fontboté, July 26, 2018, p. 17

 K2Al6(SO4)4(OH)12

Porphyry evolu-on stages

Sillitoe (2010)

L. Fontboté, July 26, 2018, p. 18

 Sillitoe (2010)

HS for instance some

polymetallic Cordilleran
or Bu]e-type veins

D veins

A-B qtz veinlets

Einaudi, M, (1996)

L. Fontboté, July 26, 2018, p. 19

 Main altera-on types-4
PropyliDc alteraDon

•  High T: Typical for deep parts of certain porphyry copper systems (e.g.
Yerington) and for IOCG

•  Albite or oligoclase (frequently after plagioclase or K-feldspar), actinolite

(frequently after Hbl and/or biotite), epidote, sphene,

•  Leaching of K, Fe and sulfides

•  It has been suggested that it is produced by saline basinal brines

Types principaux d'altéra-on-4

Altera-on propyli-que
■  External part – Almost only H2O addition, some CO2 and S.
-  Fabric preservation
-  No major chemical changes.
-  Mainly, chlorite, epidote, carbonate, pyrite, some albite, K-feldspath.
-  transition to not altered rocks and/or to rocks affected burial
metamorphism (green schist facies).

Granodiorite with propyliDc alteraDon. Note the preserved fabric. Sierra Gorda, Northern Chile, width: 0.4 mm

L. Fontboté, July 26, 2018, p. 20

 Main altera-on types-5
Na-Ca AlteraDon

•  High T: Typical for deep parts of certain porphyry copper systems (e.g.
Yerington) and for IOCG

•  Albite or oligoclase (frequently after plagioclase or K-feldspar), actinolite

(frequently after Hbl and/or biotite), epidote, sphene,

•  Leaching of K, Fe and sulfides

•  It has been suggested that it is produced by saline basinal brines

actinolite

albite-oligoclase rims

FUS-93-8 © L. Fontboté (2003)

L. Fontboté, July 26, 2018, p. 21

 Altera-on example: The porphyry system

Kouzmanov and Pokrovski, 2012

Main altera-on types in felsic igneous rocks

(M. Einaudi, 1996, unpubl.)
NOTE: all alteration types refer to envelopes on veins or volumes of rocks in which
envelopes have coalesced or in which alteration is pervasive. Reference is not to
large volumes of rocks which may reflect numerous different alteration events.

Dominant mineral are in bold letters

includes Na-Ca

L. Fontboté, July 26, 2018, p. 22

 Main altera-on types in felsic igneous rocks - 2

intermed argillic (IA) mtm, kao, chl, cly, (ser, plg -> mtm (kao); mfcs - A weak form of hydrolysis. Common
epi, py) > chl; ksp is stable or supergene assemblage; much of the IA
metastable; alt’n thought to be hyopogene in porph
deposits (e..g., Lowell & Guilbert)
probably is supergene. Note the general
absence of SE/IA envelopes on porphyry-
style “D-vns”.
sericitic (SE ou S) ser-qtz-py, chl, ill, hem mtm (kao) -> ser; ksp -> whether SE or IA depends on alt’n state of
ser (qtz); chl -> ser-py ksp; if ksp gone, then SE, but don’t forget
the scale factor--I’m referring to alt’n
along individual fract’s or vnlt’s. In
epithermal systems, SE is dominated by
ill.
adv’d argillic (AA) kao, pyo, qtz, sil, chd, ser -> kaol/pyroph; ser - The most intense form of hydrolysis (H-
py, hem, alu, (dik, zuy, > alunite; commonly metasomatism). Mention of kaol alone
adl, toz, tou, dia, cor) abundant py won’t do it, for it could be supergene or
part of an IA assemblage. Alunite is a
common campanion of AA, but again do
not rely on this phase for classification for
it could be supergene. In peraluminous
granitoids, intense hydrolysis starts at
higher T (greisens).

musc

LS, shallow (<300-400 m)

<220-230 C
IS, deeper (~300-800 m)
J. Hedenquist
>220-230 C)

L. Fontboté, July 26, 2018, p. 23

 Silication
Typic for skarn
■  CaMg(CO3)2 + 2SiO2 = (CaMg)Si2O6 + 2CO2

dolomite diopside
■  CaCO3 + SiO2 = CaSiO3 + CO2

calcite wollastonite

■  Silication + Fe and Al
■  2FeO(aq) + 3SiO2(aq) + 3CaCO3 + 1/2O2 -> Ca3Fe2(SiO4)3 + 3CO2
andradite
■  Al2O3(aq) + 3SiO2(aq) + 3CaCO3 -> Ca3Al2(SiO4)3 + 3CO2
grossulaire
■  Question: does low pH favors these reactions?

Salite (clinopyroxene group. Ca (Mg,Fe)Si2)

L. Fontboté, July 26, 2018, p. 24
 Problem with Na-Calcic!

modified from Leach and Corbep, 1998 in Wade et al. Sout Austral AGeol Surv 2015

Main messages:
■ Altera-on gives informa-on on mineralizing
fluids: pH, redox state, T….
■ Look at cross-cuKng rela-onships and
zoning!
■ Remember: altera-on gives informa-on on
the fluid chemistry directly in the field!

L. Fontboté, July 26, 2018, p. 25